ASTM C25.27147

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principlesfor the Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee. Designation: C25 − 11´2 Standard Test Methods for Chemical Analysis of Limestone, Quicklime, and Hydrated Lime1 This standard is issued under the fixed designation C25; 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 epsilon (´) indicates an editorial change since the last revision or reapproval. This standard has been approved for use by agencies of the U.S. Department of Defense. ε1 NOTE—Revised 28.3.5 editorially for clarity in May 2016. 1. Scope Carbon Dioxide by Standard 22 Method 1.1 These test methods cover the chemical analysis of Combined Oxides of Iron and 12 high-calcium and dolomitic limestone, quicklime, and hy- Aluminum drated lime. These test methods are classified as either standard Ferrous Iron Appendix X5 Free Calcium Oxide Appendix X6 (preferred) or alternative (optional). Free Moisture in Hydrated Lime 21 Free Moisture in Limestone 20 1.2 The standard test methods are those that employ classi- Free Silica 29 cal gravimetric or volumetric analytical procedures and are Insoluble Matter Including Silicon Dioxide: typically those required for referee analyses where chemical Standard Method 8 Optional Perchloric Acid Method 9 specification requirements are an essential part of contractual Insoluble Matter Other Than Silicon 11 agreement between buyer and seller. Dioxide Loss on Ignition 19 1.3 Alternative or optional test methods are provided for Magnesium Oxide 18 those who wish to use procedures shorter or more convenient Manganese: than the standard methods for the routine determinations of Bismuthate Method Appendix X4 Periodate (Photometric) Method 27 certain constituents. Optional test methods may sometimes be pH Determination of Alkaline Earth 34 preferred to the standard test methods, but frequently the use of Solutions Phosphorus: modern and expensive instrumentation is indicated which may Titrimetric Method Appendix X3 not be accessible to everyone. Therefore, the use of these test Molybdovanadate Method 26 methods must be left to the discretion of each laboratory. Silicon Dioxide 10 Strontium Oxide Appendix X2 1.4 The analytical procedures appear in the following order: Sulfur Trioxide 23 Total Carbon: Section Direct Combustion-Thermal 32 Aluminum Oxide 15 Conductivity Cell Method Available Lime Index 28 Total Carbon and Sulfur: Calcium and Magnesium Oxide: Combustion/Infrared Detection 35 Alternative EDTA Titration 31 Method Method Total Iron: Calcium Carbonate Equivalent 33 Standard Method, Potassium 13 Calcium Oxide: Dichromate Titration Gravimetric Method 16 Potassium Permanganate Appendix X1 Volumetric Method 17 Titration Method Ortho-Phenanthroline, 14 Photometric Method 1 These test methods are under the jurisdiction of ASTM Committee C07 on Total Sulfur: Lime and Limestone and are the direct responsibility of Subcommittee C07.05 on Sodium Carbonate Fusion 24 Chemical Tests. Combustion-Iodate Titration 25 Current edition approved June 1, 2011. Published May 2016. Originally Method approved in 1919. Last previous edition approved in 2011 as C25 – 11ε1. DOI: Unhydrated Oxides 30 10.1520/C0025-11E02. Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States Copyright by ASTM Int'l (all rights reserved); Thu Jun 8 19:00:12 EDT 2017 1 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. No further reproductions authorized. C25 − 11´2 1.5 This standard does not purport to address all of the extremely dependent upon precautions taken during sample safety concerns, if any, associated with its use. It is the preparation and analysis to minimize excessive exposure to responsibility of the user of this standard to establish appro- ambient conditions. priate safety and health practices and determine the applica- NOTE 1—These test methods can be applied to other calcareous bility of regulatory limitations prior to use. For specific materials if provisions are made to compensate for known interferences. precautionary statements, see 9.3, 10.2.1, 18.4.3, 31.6.4.2, X2.3.1, and X5.4.1.1. 5. General Apparatus and Materials and Reagents 5.1 General Apparatus and Materials: 2. Referenced Documents 5.1.1 Balance—The balance shall be of an analytical type 2.1 ASTM Standards:2 with a capacity not to exceed 200 g. It may be of conventional C50 Practice for Sampling, Sample Preparation, Packaging, design or it may be a constant-load, direct-reading type. It shall and Marking of Lime and Limestone Products be capable of reproducing weighings within 0.0002 g with an C51 Terminology Relating to Lime and Limestone (as used accuracy of 6 0.0002 g. Rapid weighing devices that may be by the Industry) provided such as a chain, damper, or heavy riders shall not C911 Specification for Quicklime, Hydrated Lime, and increase the basic inaccuracy by more than 0.0001 g at any Limestone for Selected Chemical and Industrial Uses reading and with any load within the rated capacity of the D1193 Specification for Reagent Water balance. E29 Practice for Using Significant Digits in Test Data to 5.1.2 Weights—Weights used for analysis shall conform to Determine Conformance with Specifications Class S-1 requirements of the National Institute of Standards E50 Practices for Apparatus, Reagents, and Safety Consid- and Technology as described in NIST Circular 547.4 They shall erations for Chemical Analysis of Metals, Ores, and be checked at least once a year or when questioned, and Related Materials adjusted to within allowable tolerances for Class S-1 weights. E70 Test Method for pH of Aqueous Solutions With the All new sets of weights purchased shall have the weights of 1 Glass Electrode g and larger made of stainless steel or other corrosion-resistant E173 Practice for Conducting Interlaboratory Studies of alloy not requiring protective coating and shall meet the Methods for Chemical Analysis of Metals (Withdrawn density requirements for Class S. 1998)3 5.1.3 Glassware and Laboratory Containers—Standard E177 Practice for Use of the Terms Precision and Bias in volumetric flasks, burets, pipets, dispensers, etc., shall be ASTM Test Methods carefully selected precision grade or better and shall be E200 Practice for Preparation, Standardization, and Storage calibrated, if necessary, to meet the requirements of each of Standard and Reagent Solutions for Chemical Analysis operation. Standard-type interchangeable ground glass or TFE- E691 Practice for Conducting an Interlaboratory Study to fluorocarbon joints are recommended for all volumetric glass- Determine the Precision of a Test Method ware. Polyethylene containers are recommended for all aque- E832 Specification for Laboratory Filter Papers ous solutions of alkalies and for standard solutions where the presence of dissolved silica or alkali from the glass would be 3. Terminology objectionable. 5.1.4 Desiccators—Desiccators shall be provided with a 3.1 Definitions:Definitions—Unless otherwise specified, for good desiccant such as anhydrous magnesium perchlorate, definitions of terms used in these test methods refer to activated alumina, sulfuric acid, or phosphoric anhydride. Terminology C51. Anhydrous calcium sulfate may also be used provided it has been treated with a color-changing indicator to show when the 4. Significance and Use desiccant has lost its effectiveness. Calcium chloride and silica 4.1 These test methods provide accurate and reliable ana- gel are not satisfactory desiccants for this type of analysis. lytical procedures to determine the chemical constituents of 5.1.5 Filter Paper—Filter paper shall conform to the re- limestone, quicklime, and hydrated lime (See Note 1). The quirements of Specification E832, Type II (quantitative). Class percentages of specific constituents which determine a materi- E shall be used for coarse and gelatinous precipitates. When al’s quality or fitness for use are of significance depending medium-textured paper is required, Class F filter paper shall be upon the purpose or end use of the material. Results obtained used. When a retentive paper is needed, Class G shall be used. may be used in relation to specification requirements. Recommendations: Filter Pore Size Filter Speed Class (microns) 4.2 Because quicklime and hydrated lime quickly absorb E 20 to 25 fast speed water and carbon dioxide from the air, precision and bias are F 8 medium speed G 2.5 slow speed 5.1.6 Crucibles—Platinum crucibles and tight fitting lids 2 For referenced ASTM standards, visit the ASTM website, www.astm.org, or should preferably be made of pure unalloyed platinum and be contact ASTM Customer Service at [email protected]. For Annual Book of ASTM of 25 to 35-mL capacity. Where alloyed platinum is used for Standards volume information, refer to the standard’s Document Summary page on the ASTM website. 3 4 The last approved version of this historical standard is referenced on Available from National Institute of Standards and Technology (NIST), 100 www.astm.org. Bureau Dr., Stop 3460, Gaithersburg, MD 20899-3460. Copyright by ASTM Int'l (all rights reserved); Thu Jun 8 19:00:12 EDT 2017 2 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. No further reproductions authorized. C25 − 11´2 greater stiffness or to obviate sticking of fused material to 6. General Procedures crucible or lid, the alloyed platinum should not decrease in 6.1 Sampling—Samples of lime and limestone for chemical weight by more than 0.2 mg when heated at 1200 °C for 1 h. analysis shall be taken and prepared in accordance with the 5.1.7 Muffle Furnace—The electric muffle furnace should be requirements of Practice C50 applicable to the material to be capable of continuous operation up to 1000 °C and be capable tested. of intermittent operation at higher temperatures if required. It should have an indicating pyrometer accurate to 6 25 °C. 6.2 Tared or Weighed Crucibles—The tare weight of cru- cibles shall be determined by preheating the empty crucible to 5.2 Reagents: constant weight at the same temperature and under the same 5.2.1 Purity of Reagents—Reagent grade chemicals shall be conditions as shall be used for the final ignition of a residue and used in all tests. Unless otherwise indicated, it is intended that cooling in a desiccator for the same period of time used for the all reagents shall conform to the specifications of the Commit- crucible containing the residue. tee on Analytical Reagents of the American Chemical Society5 where such specifications are available. Other grades may be 6.3 Constancy of Weight of Ignited Residue—To definitely used provided it is first ascertained that the reagent is of establish the constancy of weight of the ignited residue, the sufficiently high purity to permit its use without lessening the residue and container shall be ignited at the specified tempera- accuracy of the determination. In addition to this, it is desirable ture and time, cooled to room temperature in a desiccator, and in many cases for the analyst to ensure the accuracy of his weighed. The residue and container shall then be reheated for results by running blanks or checking against a comparable at least 30 min at the same temperature, cooled in a desiccator sample of known composition. for the same period of time, and reweighed. Additional ignition 5.2.2 Purity of Water—Unless otherwise indicated, refer- periods may be required until two consecutive weights do not ences to water are understood to mean distilled water or other differ by more than 0.2 mg, at which time it shall be considered water of equivalent purity. Water conforming to Specification that constant weight has been attained. For ignition loss, each D1193 meets these requirements. reheating period shall be 5 min. 5.2.3 Concentration of Reagents: 6.4 Calculation: 5.2.3.1 Concentrated Acids and Ammonium Hydroxide— 6.4.1 The calculations included in the individual procedures When acids and ammonium hydroxide are specified by name sometimes assume that the exact weight specified has been or chemical formula only, it shall be understood that concen- used. Accurately weighed samples which are approximately trated reagents approximating the following specific gravities but not exactly equal to the weight specified may be used or concentrations are intended: provided appropriate corrections are made in the calculation. Acetic acid (HC2H3O2) 99.5 % Unless otherwise stated, weights of all samples and residues Hydrochloric acid (HCl) sp gr 1.19 Hydrofluoric acid (HF) 48 % should be recorded to the nearest 0.0001 g. Nitric acid (HNO3) sp gr 1.42 6.4.2 In all mathematical operations on a set of observed Perchloric acid (HClO4) 70 % Phosphoric acid (H3PO4) 85 % values, the equivalent of two more places of figures than in the Sulfuric acid (H2SO4) sp gr 1.84 single observed values shall be retained. For example, if Ammonium hydroxide (NH4OH) sp gr 0.90 observed values are read or determined to the nearest 0.1 mg, 5.2.3.2 Dilute Reagents—The concentration of dilute acids carry numbers to the nearest 0.001 mg in calculation. and NH4OH except when standardized, are specified as a ratio 6.5 Rounding Figures—Rounding figures to the nearest stating the number of measured volumes of the concentrated significant place required in the report should be done after the reagent to be diluted with a given number of measured volumes calculations are completed, in order to keep the final results of water. In conformance with international practice, new and free from calculation errors. The rounding procedure should revised methods will use the “plus” designation instead of the follow the principle outlined in Practice E29. ratio (:) symbol as the specified designation of dilution; for example, H2SO4 (5 + 95) means 5 volumes of concentrated 7. Performance Requirements for Test Methods H2SO4 (sp gr 1.84) diluted with 95 volumes of water. 5.2.3.3 Standard Solutions—Concentrations of standard so- 7.1 Referee Analyses—The reference test methods that ap- lutions shall be expressed as normalities (N) or as equivalents pear in Sections 8 through 32, or any other test methods in grams per millilitre of the component to be determined, for qualified in accordance with 7.3, are required for referee example: 0.1 N K2Cr2O7 solution (1 mL = 0.004 g Fe2O3). The analysis in those cases where conformance to the requirements average of at least three determinations shall be used for all of a chemical specification are questioned. In these cases a standardizations. The standardization used to determine the limestone, quicklime, or hydrated lime shall not be rejected for strength of the standard solutions is described in the text under failure to conform to chemical requirements unless all sample each of the appropriate procedures. preparation and analysis of any one constituent is made entirely by reference test methods prescribed in the appropriate sections 5 Reagent Chemicals, American Chemical Society Specifications, American of this test method or by other qualified test methods. Excep- Chemical Society, Washington, DC. For suggestions on the testing of reagents not tion can be made when specific test methods are prescribed in listed by the American Chemical Society, see Analar Standards for Laboratory the standard specification for the limestone, quicklime, or Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmacopeia Convention, Inc. (USPC), Rockville, hydrated lime in question. The test methods actually used for MD. the analysis shall be designated. Copyright by ASTM Int'l (all rights reserved); Thu Jun 8 19:00:12 EDT 2017 3 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. No further reproductions authorized. 3 Demonstrations shall be made by analysis of each nation. The final results should include the number of C (lime and hydrated 0.15 ± 0. a 7. (Column 3) NOTE 4—It is not intended that the use of reference test methods be (Column 2) Maximum Difference of Maximum the Average of confined to referee analysis. No further reproductions authorized.3.2 Optional Analyses—The alternative test methods. as run on different days. quicklime.30 to the discretion of the analyst when using the alternative test Mg as MgO 0. only the differences between limestone. upon request any constituent of limestone.1 Definition and Scope—When analytical data obtained S 0. more complex procedures have been retained Table 1. supplies. . or certification of a 7. the percentages shall be product being tested.60 ± 0.3. in analysis of the limestone.5 In questions concerning the acceptance or rejection of limestone. The same test methods to be used for opposed to reference methods. generally accepted accuracy standard for that constituent has onstrations may be made concurrently with analysis of the not been identified.3.1. A test overall composition to the limestone shall be used (See Table 2). instrument. its normal matrix. Copyright by ASTM Int'l (all rights reserved). or except when demonstrated under 7.2 Test results from Referee methods intended for use as 7.05 Sr as SrO 0. determinations for each constituent may differ from the SRM er’s certification.20 ± 0. In the case of method is considered to consist of the specific procedures.1. Thu Jun 8 19:00:12 EDT 2017 4 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. quicklime. or for manufactur.1. When analyzing a quicklime or hydrated lime the SRM in variation.2.20 ± 0. can be used only after demonstration of certificate value by no more than the value shown in Column precise and accurate analyses by meeting the requirements of 3 of Table 1. If the two results do not duplicate results do agree within the permissible variation. or hydrated lime (See Notes 2 and 3). quicklime.20 ± 0. in duplicate until the results agree within the permissible NOTE 3—There are no SRMs that are quicklime or hydrated lime as variation. the NOTE 2—The term SRM refers to approved Standard Reference determination including sample preparation shall be repeated Materials listed in Table 2.20 ± 0. as alternative test methods to permit comparison of results by different procedures or for use when unusual materials are being examined. immediately prior to analysis and protect it from calculated to one more significant figure than reported as hydration or carbonation with sealed containers and desiccation during indicated in the test methods. shorter or more convenient to use for routine tested shall be used for analysis of the SRM. their average shall be accepted as the correct value. Such dem. used in a consistent manner by a specific laboratory.1 If more than one instrument is used for the same accuracy can be demonstrated. Constituent Duplicates ValuesB 7.30 Ca as CaO 0. or hydrated lime data shall be made available to all parties involved demonstrat- product for which a standard exists. quicklime. In some results do not agree within the permissible variation given in instances longer.3 Performance Requirements for Alternative Test Meth- Mn 0. When no SRM certificate value is given. but may be made for a limestone. constituent of concern in a SRM limestone. A reference test (Column 1) Between from SRM Certificate method must be used where an alternative test method is not provided. after heating at 1000 °C for 1 h. Fe as Fe2O3 0. If the duplicate determination of some constituents (See Note 4).1. C No SRM currently available.15 Si as SiO2 0. quicklime or hydrated lime.30 determinations performed and whether or not they were lime) C (limestone) 0. samples by the same analyst making the acceptance determi- 7.1.2. the SRM closest in overall composition. When a blank determination is cooling. following iden. provide procedures that are.10 ods: P 0. one shall be made with each individual analysis or converted SRM unsuitable as a standard for carbon and sulfur determi- with each group of two or more samples analyzed on the same nations. 7. A reference test method may be used in Difference Duplicates preference to an alternative test method when so desired. referee tification and correction of problems or errors. quicklime.05 C 7.05 ± 0. For carbon and sulfur determinations use the appropriate SRM in day for a given constituent.30 7.1. quicklime. except for C and S reagents.1 When there is a question regarding acceptance.3.10 ± 0. used as a basis for acceptance. equipment. or hydrated lime being some cases. etc. or hydrated lime product being tested.30 methods. or when unusual preparation for analysis is required. agree within the permissible variation given in Table 1.03 ± 0. selected and determinations (See Note 3).4 The average of the results of acceptable duplicate a basis for product acceptance or rejection. rendering the specified.05 in accordance with this section is required. any test method A For demonstrating the performance of rapid test methods the SRM closest in may be used that meets the requirements of 7. use of each instrument shall constitute a separate test method and each must be qualified separately. When the results agree within the permissible supplied.3 shall apply and notifica- The demonstration is required only for those constituents being tion of this exception shall be reported.1. duplicate values as specified in 7. B Interelement corrections may be used for any standardization provided improved 7.1 Duplicate analyses and blank determinations are left Al as Al2O3 0.2. or hydrated lime. Such demonstrations must ing that precise and accurate results were obtained with SRM be made annually.1. In such cases. to the product composition shall be used. the determinations shall be repeated. until a set of analyses shall be made in duplicate. analysis. Carbon and sulfur may be driven off during heating. or hydrated lime product. To accomplish this conversion. Results from alternative test methods may be used as TABLE 1 Maximum Permissible Variations in ResultsA a basis for acceptance or rejection. Duplicate samples shall be 7. C25 − 11´2 7. rejection.02 ± 0.3.60 corrected for blank values.1. carbonate form needs to be converted to closely resemble the matrix of the For the purpose of comparing results. heat the chosen SRM for 1 h at 1000 °C. 17 0. critical components of an instrument essential to the test NOTE 5—An actual drawing of a curve is not required. No further reproductions authorized. quicklime.22 0.60 20.15 0.02 NC 43.55 52. or is significantly qualified alternative test methods shall be indicated as having modified. For example. only for those components for which acceptable results are obtained.092 0.3.2.57 GBW 07215 0.013 0.96 0.3.019 0.3.030 NC 0.24 53.226 0.3.67 0. The qualification testing shall be constituents. as when conducted with newly prepared specimens.017 NC 0. saw-tooth curve that NOTE 6—Instrumental analyses can usually detect only the element is artificially made to fit a set of data points does not constitute a valid sought.022 0.3. if it be carried out prior to further use of the method for analysis of has been determined that blank values do not affect the validity those constituents.98 0.017 54. Thu Jun 8 19:00:12 EDT 2017 5 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.33 50. The use of private stock. Qualification data or.024 NC 0.0055 0.22 GBW 07216 0.07 0. make single determi- 7.0012 NC 0.55 16.040 0. providing data in accordance with Table 1 shall be considered 7.99 0.52 IPT 48 0.009 0.04 1. C25 − 11´2 TABLE 2 Approved SRM List Na as Al as % Ca as % Mg as % Fe as % Si as % Sr as % Ti as % K as % % (SRM) Al2O3 CaO MgO Fe2O3 SiO2 % Mn %P SrO %S TiO2 K2O Na2O % L.84 0.174 NC NC NC 46.024 41.1 Using the test method chosen. which in overall composition most closely resembles the limestone.14 0.97 3.3.071 0.011 0.014 NC NC NC 46. Complete two rounds of tests on nonconsecutive days substantial evidence that the test method may not be providing repeating all steps of sample preparations. the actual procedure used for the curve-fitting procedure.029 (46.05 NC 0.9 A This SRM is still available.2 The differences between duplicates obtained for any to have been received when a laboratory is informed that single constituent shall not exceed the limits shown in Column analysis of the same material by Reference Test Methods run in 2 of Table 1. may be used by Wet Test should be compared to the sum of Fe2O3 and Al2O3 obtained instrumentally. corrections shall be made for 7.17 31.016)D 0.2 Qualification of a Test Method—Prior to use each test been obtained by alternative methods and the type of test method (See 7.004 43.28 0. is not needed for the method in use.048 0.92 0.23 0.2.014 0.5 Rejection of Material—See 7.2.2 0. nations for each constituent under consideration on the SRM shall be required annually.4 The standardization. ECRM-752-1A 0.14 1.69 0.2 Requalification also shall be required upon receipt of 2).0 0.23 0.17 0. as defined in 7.4 If an instrument or piece of equipment is replaced 7.9 NIST 88B 0.022 0.6 Requalification of a Test Method: 7. accordance with 7.12 0.0089 NC <0.98) BCS 368 0.10 0.3. be tested.292 1. C This SRM has been found to be unavailable commercially.40 30.002 0. requalification 7.42 0.006 NC 0.70 0.30 2.45 0.69 0.1 Requalification of a test method.2.93 0.012 0.070 41.9 0.020 NC NC NC 43.196 NC NC NC 43.55 6. data shall be made available.38 2. 7.0013 NC 0.63 1. .5 2.51 0. When indirect test methods are involved.04 NC 0.022 NC NC NC GBW 07214 0.003 0.3 Partial Results—Test methods that provide acceptable procedures exist. D ( ) = not certified.006 0.3 For each constituent the average of the duplicates or an accepted value of a known secondary standard differs obtained shall be compared to the SRM Certificate value and from the value obtained by the test method in question by more shall not differ from the certified value by more than the value than twice the value of Column 2 of Table 1 for one or more in Column 3 of Table 1.9 IRSID DO 1-1C 0. B NC = not certified.3 0.6.030 NC NC NC NIST 1C 1.6.009 0.013 46.027 36.006 0.295 30.30 50.034 0. 7.103 0. if such a curve method.3.3.006 0.13 0.3. a certified value of an approved SRM.007 0.0011 NC 0.629 2.01 NC (<0.017 0. or hydrated lime to be tested (See Note 7.0018 NC 0.34 29.30 GBW 03106 0. but its name has been changed from BCS 393 to ECRM 752-1. a test method also shall be requalified shall be performed as frequently as required to ensure that the after any substantial repair or replacement of one or more accuracy and precision in Table 1 are maintained. though.70 0.I.0 21.1.95 21.019 0.8 20.28 0.6.15 0.88 47.4 0.098 0.8 0.56 2. used for qualifi.2. 7.64 50.277 1.6.59 0.95 0.007 0.008 NCB 0.01) 46. if applicable.7 IRSID 702-1 0.23 GBW 07217 0. Therefore. Combined Oxides of Iron and Aluminum results for some constituents.3. Restandardization constituents affected.0096 0. of the data.60 1.05 20. 7.04 NC 0.3. a previously qualified test method using such new or Copyright by ASTM Int'l (all rights reserved).2.3. For any valid curve-fitting procedures (See Note 5). elemental analysis should be noted when differences with reference 7.3.49 3.1 and 7.17 30.14 0. but not for others.002 42.38 0. Such requalification may be differences between values and the averages of values from the limited to those constituents indicated to be in error and shall two rounds of tests.29 4.376 0.84 0.38 0. Blank determinations are not required.026 0.045 0.67 0.012 0.009 NC 0.036 0. Calculate the data in accordance with Table 1.3. A point-to-point. Blank or interference-corrected data must be so 7.O.019 0.4 Report of Results—Chemical analyses obtained by even by one of identical make and model. data for information only.1.58 GBW 03108 0. minor constituents in order to put the analyses on a comparable cation and analysis of each constituent shall be determined by basis prior to determining the differences (See Note 6). if applicable.73 0. a value is obtained by difference.4 IPT 35 0.022 NC 0.027 0. is still allowed.020 39.1) must be qualified for each material that will method used shall be designated. to avoid controversy.0076 NC (0.3 Substantial evidence that a test method may not be designated.50 51.12 55.0 IPT 44 0. preferably of platinum (See standard method except that perchloric acid is used to dehy- Note 9). ignite in a Perchloric Acid Method) covered platinum crucible in an electric muffle (See Note 8) at 9. aluminum.3. glass container positively must not be used. burned off. barytes. Insoluble Matter Including Silicon Dioxide (Standard and then ignite at 1000 °C for 30 min in an electric muffle Method) furnace (See Note 8). Thu Jun 8 19:00:12 EDT 2017 6 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.3 Procedure: adequate for the contemplated use. Cool in a desiccator and weigh. calcium. increase in weight represents the insoluble matter including tion to dryness of the hydrochloric acid solution of the SiO2. remove the dish from the heat.4 Precision and Bias—Different analytical test methods solution for 1 to 2 min. nations. Any organic matter in the containing the insoluble residue through a retentive filter of sample must first be destroyed by the addition of nitric acid suitable size.2 Evaporate the solution to dryness on a steam bath. porcelain may be used. diluted (HNO3) to the sample prior to fuming with HClO4. No further reproductions authorized.1 Weigh 0. The two bias statements within standards was mandated.5 g of sample. The 8. tourmaline. combine the two wet papers containing the separated residues and transfer to a weighed platinum crucible.01 % as follows: limestone consists of free silica and a mixture of minerals such as clay. but this time heat the acidified 7. The acid-insoluble residue of a typical ter including silicon dioxide to the nearest 0.1 Scope—This test method is based on a double evapora. the silica is dehydrated by a double evaporation to B = original mass of sample.2 Summary of Test Method—After dissolution in hydro. Insoluble Matter Including Silicon Dioxide (Optional If the sample is a limestone or hydrated lime.3. Retain the responsibility of the user to demonstrate that the test methods filtrate for iron. The user is papers containing the residues are combined. and chloric acid.0 g of limestone ground to pass a No. if weighed.2. 9. samples must be protected the insoluble silicon dioxide in less than 20 min. NOTE 8—Ignition of the sample in an electric muffle is far superior to flame ignition. However. without prior ignition by a mixture of nitric (HNO3) and NOTE 9—If a platinum dish is not available. available. All (5 + 95) HCl and then twice with hot water. flame 9. the resultant ash is ignited at high temperature until When dry or nearly so. mix to a thin slurry. Insoluble matter including SiO2 5 ~ A/B ! 3 100 (1) rutile.3. Wash filter thoroughly with warm. 8. the loss on ignition (LOI) can be determined first. 8. there are pre- allow the dish and contents to cool slightly. the dry salts are redissolved 8. may lead to serious 8. sary. Fuming perchloric acid is a very powerful dehydrating NOTE 7—Due to the rapidity with which quicklime and hydrated lime agent. The insoluble matter including silicon dioxide a short period of time to completely dehydrate the silica. garnet. dehydrate and extract method and must be qualified in accordance with 7. The fuming perchloric acid is refluxed at this temperature for NOTE 10—Alternatively. A = mass of ignited residue. 50 (250-µm) sieve (See Note 7). cautions to be followed which.3. The can then be assayed using the ignited product that remains in the LOI residue of silica and insoluble matter is filtered and washed free crucible. Filter through a second and smaller are subject to individual limits of precision and bias. using 0. This test in tightly stoppered containers at all times. 8. When using HClO4. mica. 9. etc. and then is weighed. dryness. and extremely reactive liquid. and silicic acid can usually be completely converted to absorb water and carbon dioxide from the air.3 Procedure: Warning—Perchloric acid (HClO4) is an Heat for 1 h at 100 °C.5 g of quicklime or hydrated lime. ignited.4 Evaporate the filtrate to dryness. ing silicon dioxide is determined gravimetrically as in the Transfer to an evaporating dish. C25 − 11´2 modified instrument or equipment shall be considered a new 8. Samples for analysis are to be method has been determined by other agencies such as the weighed quickly and the sample container re-stoppered immediately after Association of Official Agricultural Chemists (AOAC) to be the sample has been removed. Contact of the hot concentrated acid with organic place on the water bath for 10 min. ventilated hood made of nonporous and inorganic material. comparable to the standard hydrochloric acid method. Copyright by ASTM Int'l (all rights reserved). and cautioned to verify by the use of reference materials. The filter paper containing the residue is 8. limestone or lime sample to convert silicon dioxide (SiO2) to 8. Reserve the paper evaporations involving HClO4 must be done in a well- and residue. containing about 10 mL of water. and digest with the aid of gentle heat standard method because only a single dehydration is neces- and agitation until solution is complete (See Note 10). The procedure is more rapid than in the add 5 to 10 mL of HCl.3. where: 8. of acids and salts.4 Calculation—Calculate the percentage of insoluble mat- the insoluble form. the solution is filtered. g. the residue with HCl as before. It is the piece of retentive filter paper and wash as before. g.3 Drench the cooled mass with 20 mL (1 + 1) HCl and explosions. After each dehydration. feldspar. cover the dish and place it in an air bath the ash is white.5 Precision and Bias—This test method was originally with dilute hydrochloric acid.1 Scope—In this test method the insoluble matter includ- 950 °C for 15 min or longer to effect complete decomposition.3. and magnesium determi- used at least meet the requirements shown in Table 1. and the approved for publication before the inclusion of precision and siliceous residue and other insoluble matter separated. or drying oven or on a metal triangle resting on a hot plate. zircon. . if an electric muffle is not available. that the precision and bias of this test method are 8. or 1. drate the silica. A perchloric (HClO4) acids and evaporated to fumes of HClO4.2 Summary of Test Method—The sample is decomposed ignition and the blast lamp may be used. if unheeded.5 Char carefully without allowing the paper to inflame. Filter the mixture matter must be absolutely avoided. 210 18 MgO (Gravimetric) 21.204 12 Combined Oxides 0.36 0.2 With the beaker covered.6–43.4 Place the filter paper and contents in a weighed goggles should be worn when using this acid.558 1. (Standard) 9 Insol + SiO2 1.1 Scope—For control purposes or routine 9.371 1. silicon dioxide repeat the dehydration.3. 50 (250-µm) sieve. heat to boiling. and dissolve cautiously with 10 mL of concentrated adequate for the contemplated use.34 21.2 The user is cautioned to verify by the use of reference sample to a 250-mL beaker. Copyright by ASTM Int'l (all rights reserved).2 Procedure: pH paper until washings are free of acid (See Note 11).28 0. % 5 ~ A/B ! 3 100 (2) mass of SiO2.. % 5 ~ @ A 2 B ! / C# 3 100 (3) TABLE 3 Precision Summary of Classical Test Methods Average. for certain applications in process industries.183 15 Al2O3 0. an additional eight limestone samples thereby obtaining the 9. harmful to eyes and skin. g. rubber gloves and 9.46 53. Reserve 10. may be determined by volatilizing the SiO2 from the insoluble 9. calcium.3. a separate analysis of SiO2 may not be neces- completely dehydrate the silica. g. add 50 mL of water. It does its work platinum or porcelain crucible and heat gently with a low flame silently and leaves a festering sore that is slow to heal.132 17 CaO (Volumetric) 53. become solid or go to dryness.6–55. This is a very crucible when the filter paper is charred and ignited.1 To the ignited residue in the platinum crucible (See the filtrate for iron.5 or 9.09–6. Thu Jun 8 19:00:12 EDT 2017 7 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.93 0.2. Add 20 mL of perchloric acid and boil until dense white fumes appear. Wash paper and by the difference in mass obtained.165 0.817 0. To satisfy situations such as this. 10.21 0. immediately if any acid is sprayed into the eyes or if prolonged ignite at 1000 °C for 30 min. or 1 g of precision data summarized in Table 3. and 1 or 2 drops of H2SO4. However.03–5.7 0..2.2 Evaporate to dryness on a hot plate and heat in an 9. Silicon Dioxide several millilitres of HNO3 until the solution clears. . Never allow contents to sary.82 49..5. Any until paper chars without inflaming. A physician should be notified until the carbon has been burned and the ash is white. The difference between this mass and the mass of insoluble matter including silicon dioxide is the Insoluble matter including SiO2 . If this happens. Slowly raise the temperature with copious quantities of water.02–0.268 0.3.36 0. C25 − 11´2 preferably Type 316L stainless steel.169 0. wet carefully with a few millilitres materials. Cool in ter including silicon dioxide to the nearest 0. Test with 10.1 0.184 0.3 Cool.463 A Average and range of the limestones tested. dangerous acid.187 0.A Range. These precautions on perchloric acid stone samples and three laboratories cooperated in testing on use are fully discussed in Practices E50.652 1. but extra perchlorate salts to prevent small explosions from occurring in the precaution is required with hydrofluoric acid.180 0.020 17 CaO (Volumetric) 30.A % Repeatability Reproducibility Section Test Method % Found Found (R1.10–0.146 11 Insoluble Matter 0. Finally.1 Four laboratories cooperated in testing on four lime- regularly and thoroughly.3 0.22–1.242 0.298 18 MgO (Gravimetric) 0. If the solution darkens at this point. nitric acid.282 13 Fe2O3 0.351 (Optional) 10 SiO2 1. and magnesium 8. SiO2 . limestone ground to pass a No. aluminum. residue thoroughly (at least 15 times) with hot water.01 % as follows: a desiccator and weigh. insoluble matter including SiO2. Transfer the 9.1 Weigh 0.1–21. or alternatively char in an acid that touches the skin should be immediately washed off electric muffle at 300 to 400 °C.5. that the bias of this test method is of water.3.405 0. NOTE 11—The filter paper and silica residue must be washed free of Warning—All acids should be handled with care.57 30.4).73 43. where: 10. Cool in a desiccator and weigh as contact with the skin occurs.223 16 CaO (Gravimetric) 54. add more HClO4 and be important.181 0. 5 mL of hydrofluoric acid determinations. Heat again to fumes. if available.5 Precision and Bias: provided for washdown procedures that should be performed 9. Facilities should be 9..05–0..19–2. .177 0.9 0. add 10.4–55. (HF).3. E173) (R2. . 10.40 0.716 19 Loss on Ignition 43. and filter residue with hydrofluoric acid and the percent SiO2 determined immediately using medium textured paper.. E173) 8 Insol + SiO2 . boil gently for 15 min to determinations. electric muffle at 1000 °C (See Note 8) for 2 or 3 min.5 g of quicklime or hydrated lime.459 0..88 0. add 5 mL of water..5 0. and to the nearest 0.3 Calculation—Calculate the percent of silicon dioxide A = mass of ignited residue.01 % as follows: B = original mass of sample.158 0. . No further reproductions authorized. otherwise the separation of the amount of silica derived from the lime or limestone could silica will be incomplete.4 Calculation—Calculate the percentage of insoluble mat.064 0.3.4–30.158 0.128 0. % 5 A 2 B (4) a few drops of methyl red solution. and manganese oxide (Mn3O4) 10.5 Precision and Bias: precipitate to settle (not more than 5 min). siliceous minerals.2 %)—Dissolve 2 g of methyl after the silica is volatilized with HF may be dissolved by red indicator with 1 L of 95 % ethyl alcohol. add Insoluble matter other than SiO2 . may then be ignited to their respective oxides. %. and heat just to boiling.4. and solution becomes distinctly yellow. %. limestone. that the bias of this test method is combined oxides are usually weighed first. The iron must then be oxidized by adding 1 matter other than silicon dioxide to the nearest 0. of the metals and the insoluble residue may be discarded. assayed separately.2 The user is cautioned to verify by the use of reference of any dissolved carbon dioxide (CO2). Insoluble Matter oxides and the percent Fe2O3. 12. fusing the residue with 2 to 3 g of sodium carbonate (Na2CO3) (See Note 12). phosphorus pentoxide (P2O5). separately and appropriate corrections made in the Al2O3 The insoluble matter contains the remnants of any clay. g (insoluble matter including Titanium. Heat the solution containing the precipitate to boiling and boil for 50 to 60 s.3.3 Dilute with water to a volume of 200 to 250 mL. or a fusion made in the platinum crucible sodium carbonate. then add 1 drop in excess B = SiO2. NOTE 14—The NH4OH used to precipitate the hydroxides must be free 11. Where separate determinations are preferred. The elemental components are mainly iron and aluminum. C25 − 11´2 where: 12. If the insoluble matter hydroxide. with minor amounts of titanium dioxide (TiO2).3.4. little if any manganese will be precipi- including silica is reported as such and no hydrofluoric acid tated. or other refractory material present in 12. (1 + 1) to change the color of the solution from red to orange and another Copyright by ASTM Int'l (all rights reserved).3. then there is no need to make a recovery metal oxides. Remove from heat and allow the 11. Cool the melt and dissolve it in diluted HCl. When necessary. NOTE 13—Sufficient hydrochloric acid must be present before the NOTE 12—Fusion with pyrosulfate is to be avoided because this will solution is rendered ammoniacal to prevent the precipitation of magne- introduce undesirable sulfates into the solution. No further reproductions authorized. Boil the filtrate to follows: eliminate the excess bromine completely before adding methyl red indicator.1 Scope—The difference between the mass of insoluble generally assumed to be present in trace amounts and are often matter (including silicon dioxide) and silicon dioxide repre.1 Methyl Red Solution (0. Manganese) SiO2). it usually takes 1 drop of NH4OH adequate for the contemplated use. Thu Jun 8 19:00:12 EDT 2017 8 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. containing the HF-insoluble residue.3 Special Solution: 11. The precipitate is ignited and weighed as the combined treatment is indicated. it 10. materials.5.3). aluminum.2 Summary of Test Method—In this test method. disregarded. Aluminum.1 Scope—The combined oxides describe a group of B = mass of ignited residue less SiO2.4 or 9.2 The user is cautioned to verify by the use of reference also present.3 An alternative fusion can also be made using either 12.4 Procedure: Add the solution to the filtrate from the dehydration and 12. Combined Oxides (Iron. 11. . the materials. A = mass of ignited residue. g. The other metal oxides are 11. that the bias of this test method is NOTE 15—At the neutral point.01 % as mL of saturated bromine water to the filtrate.4.1 Three laboratories cooperated in testing on four medium-textured paper and wash the precipitate two or three limestone samples and two laboratories cooperated in testing times without delay with a hot. titanium.3. The group on an additional eight limestone samples thereby obtaining the of metal oxides consists primarily of the oxides of iron and precision data summarized in Table 3. g. iron may have been 11.5.2 If a platinum evaporating dish has been used for the lithium metaborate or lithium tetraborate as opposed to using dehydration of SiO2.4. Filter using 11. iron oxide is then adequate for the contemplated use. analysis. Phosphorus. iron. sium. add hydrochloric acid (HCl) if necessary 8. 12. Historically.4 Calculation—Calculate the percentage of insoluble partially reduced.4 or 9. where: Add NH4OH (1 + 1) (See Note 14) until the color of the A = insoluble matter including SiO2.3).4. these metals may be analyzed sents the mass of insoluble matter other than silicon dioxide. and phosphorus are precipitated aluminum which should be removed and added to the main from the filtrate after SiO2 removal. 12. by means of ammonium filtrate from the SiO2 separation. precision data summarized in Table 3. 12. (See Note 15).2 Procedure—The insoluble matter left in the crucible 12. 2 % solution of ammonium on an additional eight limestone samples thereby obtaining the chloride (NH4Cl) (See Note 16).4 Precision and Bias: has been the practice to report the combined oxides present in 10.1 Three laboratories cooperated in testing on four limestone samples as a group because it was not always easy or limestone samples and two laboratories cooperated in testing desirable to determine each metal oxide separately. and metals that form precipitates with ammonium hydroxide which C = original mass of sample.1 To the acid solution from the determination of SiO2 separation of insoluble matter including silicon dioxide (See (See 8. With care. and aluminum oxide is finally determined by calculating the difference between the percent combined 11. if available.3. if available. to ensure a total of 10 to 15 mL of HCl. pyrosulfate (K2S2O7). the final precipitate should clear melt in the crucible. 13. but could be as much 12. add 20 mL of water.01 % as ignored.4 Set aside the filtrate and dissolve any precipitate HgCl2 in 100 mL of water.0040 g Fe2O3. it has probably become oxidized to stannic chloride 13. 13.4. where: NOTE 18—When the iron is present in small quantities.2 The user is cautioned to verify by the use of test just disappears. Total Iron. If the analyst prefers to determine it. solution (See Note 20) until the yellow color of the ferric iron 12.3 Mercuric Chloride Solution (5 %)—Dissolve 5 g of 12. to 1100 °C. and wash fragments into a 9. C = original mass of sample. preserve the SnCl2 solution.5 Calculation—Calculate the percentage of ammonium appearing at this point. combined oxides by fusing the oxides with potassium pyrosul.4.1 Scope—Iron in limestone is usually present as pyrite 13. The solution should be distinctly yellow when it is of SnCl2 · 2H2O in 10 mL of HCl and dilute to 100 mL with ready to filter. and ignited. Evaporate the solution to fumes of sulfuric acid papers are charred. as 1 to 2 mg.3. heat slowly until the fused mass.1 Four laboratories cooperated in testing on four lime.6 Precision and Bias: NOTE 19—The recovered SiO2 is usually small.3.3. and warm to dissolve the salts. No further reproductions authorized. If the most if not all of the iron minerals present in the limestone ore precipitate appears gray or black.20 g sodium diphenylamine sulfonate in 100 to red at any time due to heating. Add 10 mL of mercuric chloride solution. it should be brought back to yellow by mL of water.3. Combine filtrates for Ca Note 18) in the platinum crucible. If it is not. even after two evaporations. and minerals. Add 5 mL of H2SO4 (sp 12. add 3 to 4 g of potassium and calcium magnesium analysis. Add several pieces of mossy tin metal to the bottle to (1 + 1). if available. The amount present varies according to the location allow to stand for 3 to 5 min.4 Add 5 mL of H3PO4 and 3 drops of sodium diphe- Fe2O3 content of the sample is determined from the ignited nylamine sulfonate indicator. the addition of a drop of NH4 OH (1 + 1).3). the follows: precipitate can be filtered. N)—Dry pure crystals of K2Cr2O7 at 110 °C. break up the button by gently be washed at least eight times to remove all traces of perchlorate salts (See tapping the crucible on the bench.3 Cool the mixture and add approximately 100 mL of (FeS2) with occasional occurrences of other discrete iron cold water. stir. Standard Solution (0. The iron is ing the solution slowly while stirring constantly.4 Procedure: textured filter paper and washed four or five times (See Note 13. however. 1 mL = 0. Fuse at low heat until the oxides form a NOTE 17—If perchloric acid has been used. . Add dropwise stannous chloride precision data summarized in Table 3.4518 g of (1 + 19) followed by hot water and reserve the paper. 12. The precipitate is filtered through a fresh piece of medium 13. Cool. This is a solution and precipitate the hydroxides with NH4OH as before. reference materials. If the color fades during 13. 13. primary standard. white.2 To the sulfuric acid solution.05 acid through the paper into the beaker in which the precipita. Wash the filter paper thoroughly with hot HCl and dry at 180 °C to constant weight. pouring the hot 13. There may be traces of silica 12. add 10 mL HCl (1 + 1) an additional seven limestone samples thereby obtaining the and heat to near boiling.05 N K2Cr2O7 solution add- fate and leaching the melt with sulfuric acid. 13. which for most routine work can be hydroxide group (combined oxides) to the nearest 0.1 Stannous Chloride Solution (50 g/L)—Dissolve 5 g should not be prolonged as the precipitate may peptize and be difficult to retain on the filter. The recovered SiO2 can then be added to the mass of SiO2 previously found and its mass deducted from the gross mass of iron and Combined oxides. and heat to dissolve the a weighed platinum crucible (See Note 9). restore the yellow color with more NH4OH water. g. Standard Method and a fresh supply should be obtained. Under these conditions. silky precipitate should form. C25 − 11´2 drop to change the color from orange to yellow.4 Potassium Dichromate. If the color reverts g/L)—Dissolve 0. the alternative procedure should be used with a larger sample weight.4. violet.4. and desirable to determine it in the ignited oxides from the 0. stone samples and three laboratories cooperated in testing on 13. add more of the indicator.3 Special Solutions: the precipitation or while heating.5-g sample. Cool in a desiccator and weigh. it indicates too much SnCl2 was added will be converted to iron oxide or sulfate.82) to the contents in the beaker. Store in a dark-colored bottle. The end point reduced to the ferrous state with stannous chloride and titrated is indicated by a change in color from green to deep blue- with a standard solution of potassium dichromate (K2Cr2O7). from the paper with 40 mL hot (1 + 3) HCl. and the analysis must be repeated. Cool.6.5 Place the moist precipitate and the two filter papers in gr 1. During lime calcination. The boiling 13. and finally ignite to constant weight at 1050 and fume strongly for about 10 min.4. and geological history of the deposit. small beaker with hot H2SO4 (5 + 95). then pulverize tion was made. NOTE 16—Two drops of methyl red indicator solution should be added 13. Copyright by ASTM Int'l (all rights reserved). the total 13. NOTE 20—If the stannous chloride has little effect and more than 5 to 10 mL are required. Thu Jun 8 19:00:12 EDT 2017 9 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. washed. Boil the pulverized K2Cr2O7 in water and dilute to 1 L.1 To the combined oxides of iron and aluminum (See 17) with a hot 2 % solution of NH4Cl. NOTE 21—A slight.4.4. Add 2 or 3 drops of SnCl2 in excess. that the bias of this test method is adequate for the contemplated use.2 Sodium Diphenylamine Sulfonic Acid Indicator (2 to the NH4Cl solution in the wash bottle followed by NH4OH (1 + 1) added dropwise until the color just changes to yellow.5 Titrate with standard 0. g. it is not always A = mass of the combined oxides.6.2 Summary of Test Method—In this test method. % 5 ~ A/C ! 3 100 (5) aluminum reported (See Note 18). Dissolve 2. Thu Jun 8 19:00:12 EDT 2017 10 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. Filter the insoluble required.3. curve by plotting the absorbance versus the concentration of Fe2O3 in µg/mL of solution. add. the ortho filtrate to boiling.0 mg Fe2O3)— C 3D % Fe2 O 3 5 (7) Dissolve 0. 6. respectively. Total Iron by Ortho-Phenanthroline Photometric Method 14.4. where: respectively 0. then add 1 drop an additional seven limestone samples thereby obtaining the of NH4OH (1 + 1) in excess. E.3 Special Solutions: (1 + 1) in excess. 14. and W = sample mass. 1959.1 Hydroxylamine Hydrochloride (10 g/100)—Dissolve 20 min.5 Calculation: 14. ride solution.3. 3rd Ed.4.2 The user is cautioned to verify by the use of reference solution in a spectrophotometer at a wavelength setting of 510 materials. and mixing after each addition.2 Summary of Test Method—The bulk of the iron in the water. Colorimetric Determination of Traces of Metals. For an several times with hot water. Char the forms a complex with ferrous iron. less HCl (1 + 1) and evaporate rapidly to dryness. A = K2Cr2O7 used in titration. Determine the absorbance of the solution in a 10 g of hydroxylamine hydrochloride in 100 mL of water. and an accurate analysis at this low level is HCl (1 + 4) and heat to dissolve the salts. and the insoluble matter including SiO2. 8. Add NH4OH (1 + 1) stone samples and three laboratories cooperated in testing on until the congo red indicator turns bright red.5 Calculation: 14. Dilute to 50 mL.2.1 g/100)—Dissolve 1. stand for 15 to 20 min.004 (Fe2O3 equivalent of K2Cr2O7). The color intensity is proportional to the iron content of until the carbon has been completely burned off.8. 14. Interscience Publications. and 10 mL Fe2 O 3 . Roll a small piece of congo red paper into a 13. g. which the evaporated HCl solution in a platinum crucible. that the bias of this test method is nm using water in the reference cell.6 In general.1 Iron Work Standard Solution (1 mL = 0.1 Weigh 1 g of the properly prepared sample in 10 mL 14. 5 mL of ammonium acetate. ball and insert it into the volumetric flask.2. mL H2SO4 and 10 to 15 mL HF and evaporate to fumes of sulfuric acid. Transfer the acidified sample is dissolved with HCl.4 Iron Standard Solution (1 mL = 1. 14. D = dilution factor.10 phenanthroline. 0. No further reproductions authorized. 1. Pipet the aliquot containing to expel the SiO2 and recover the small amount of iron that 0. 14.3.0 g in 1 L of hot water. the silica dehydrated and solution to the main solution containing the bulk of the iron. indicator turns a bright red. Cool. Reserve the residue. Cool. . 4.2 Place the paper containing the insoluble matter from then adding a slight excess of 1.1 Add to each flask in the following sequence.0 micrograms Fe2O3.4 Procedure: 14. Roll a color of the ferrous complex is developed with 1.3. B.1 %.10 mg Fe2O3 into a 50 mL volumetric flask. Dilute to may not have dissolved with HCl.4.7000 g of pure iron wire by heating gently in 20 mL W 3 104 of HCl (1 + 1) and dilute to 1 L in a volumetric flask. Compare against a set of standards 14.3. and warm to dissolve salts. where: 14.1 Scope—When the iron oxide content is very low. 5 mL iron is reduced with hydroxylamine hydrochloride and the ammonium acetate. The acidified solution is about 25 mL and add in the following sequence. and 2. small piece of congo red paper into a ball and insert into the throline and compared against a set of iron standards similarly volumetric flask.1 Calculate the % Fe2O3 as follows: 14. then add one drop of NH4OH 14. g. and 5 mL of 1. and let precision data summarized in Table 3. 14.5 Preparation of Calibration Curve—To each of six 50 mL volumetric flasks. separated by filtration..3.10 (Ortho) Phenanthroline (0. each mL of the prepared standard solutions will contain.10 13. L of water.1 Four laboratories cooperated in testing on four lime.01 mg Fe2O3)—Transfer 10 mL of the iron standard solution to a 1 L C = concentration of Fe2O3 in sample solution. 1.. B = 0.5. dilute the contents of the crucible with 14. giving an orange-pink paper at low heat without inflaming.4. Prepare a calibration adequate for the contemplated use. and 5 mL of 1. 1. 1 mL of hydroxylamine hydrochlo- C = sample.02 to 0. 14. it is preferable to determine iron using procedures matter including SiO2 through a retentive paper and wash that have better sensitivity than the titrimetric methods. Add 50 mL of than 0.3 Transfer the combined solutions to a 100 mL volu- ignited in a platinum crucible and treated with HF and H2SO4 metric flask and dilute to volume. µg/mL volumetric flask and dilute to volume with water.3 1. % 5 ~ A/C ! 3 B 3 100 (6) of working iron standard solution. phenanthroline method has proved invaluable.6. C25 − 11´2 13. mix and let stand for 15 to 14. (determined from calibration curve). the method consists of reducing the iron to the ferrous state and 14. mL.6 Precision and Bias: phenanthroline. spectrophotometer at a wavelength setting of 510 nm using Prepare fresh every week.2 Ammonium Acetate (20 g/100)—Dissolve 200 g in 1 similarly treated. water in the reference cell.6. add 1 the solution.10 phenan.4.3. then ignite at higher heat color. mix. Add NH4OH (1 + 1) until the congo red treated. The after each addition: 1 mL hydroxylamine hydrochloride.6.6 Precision and Bias: Copyright by ASTM Int'l (all rights reserved). 0. Determine the absorbance of the 13. mixing well transferred to a volumetric flask and diluted to volume. 6 Sandel. 10 phenanthroline. if available. 2. Dilute to 50 mL. When diluted to volume. Heat the accurate determination of minute amounts of iron.5. 0631 0.4 Procedure: S-1143 0.1 Four laboratories cooperated in testing on four lime.0466 0. Thu Jun 8 19:00:12 EDT 2017 11 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.0201 0. Test Method: Material Average Sr SR r R 16.0214 0.4. Remove from the heat and let stand until the precipi- determined.0640 0. Place the filter in a tared platinum 16.1574 0. Determinations 4 2 16.0148 0. 25 mL of hot saturated ammonium oxalate solution while bined oxides and Fe2O3. The precipi. add ammonium hydroxide (1 + 3) slowly until a precipitate begins to form. Digest.1688 0. characterized by repeatability.1 and 5.0599 acid to the combined filtrates from the iron and aluminum S-1141 0. washed.0564 16. while materials. Allow to cool 15. and determi. Cool. with a pipet) while 15. add the ammonium 15. At this point.2 Ammonium Oxalate Wash Solution (1 g/L)— Precision Statement for % Fe2O3 Color Dissolve 1 g of (NH4)2C2O4 in 1 L of water. an additional seven limestone samples thereby obtaining the wash with a hot 2 % solution of NH4Cl. their oxides must also be deducted. where: Increase the heat to burn off all the carbon and ignite at 1000 A = combined oxides (Al2O3 + Fe2O3). %. adequate for the contemplated use. 16.3 Calculation—Calculate the percent Al2O3 as follows: precipitate.0058 0. 35 mL of saturated (NH4)2C2O4 solution.3. Heat just stone samples and three laboratories cooperated in testing on to boiling. materials. Any of the NH4OH group of metals CaO.3 Special Solutions: 14. filtered. filtered.1 % solution of (NH4)2C2O4 (See Note 22). Reserve percent Al2O3.1). be reported. tate has settled and the supernatant liquid is clear.4 Precision and Bias: Add a few drops of methyl red indicator and neutralize with 15. Report the remainder as neutral 0.4. and dilute to about 100 mL with water. will partially crystallize out and the supernatant solution will and reproducibility. .1 mg of CaO. Add method. has been determined for the then be saturated with ammonium oxalate. One litre of hot water will dissolve 5 mg of CaO.1 The number of laboratories.1 Scope—Calcium is separated from magnesium by crucible with cover and carefully char the paper without means of a double precipitation as the oxalate after the inflaming.1792 S-1142 0.4.1. following test method and materials to be: 16. % 5 A 2 B (8) crucible. ignite.4.4.3 Heat the filtrate to boiling and add slowly.1 Precision.0163 0. additional data will be obtained and pro.0358 0.6. filter it. that the bias of this test method is stirring. C25 − 11´2 14.6.0562 0. of dilute HCl (1 + 4).1 Ammonium Oxalate Solution (saturated)—Dissolve Within five years.2 Summary of Test Method—Calcium is precipitated with (CaO) as follows: ammonium oxalate (NH4)2C2O4. Increase the heat to burn off the carbon and ignite determination of the ammonium hydroxide group. 15. weigh. Calcium Oxide by Gravimetric Method determination of MgO. and °C for about 10 min. cessed which does meet the requirements of Practice E691.0053 0. When phosphorus or titanium are stirring.1 % (NH4)2C2O4 solution will dissolve only 0. No further reproductions authorized. filter. and add precision data summarized in Table 3.1. ignited to the oxide.2. is considered to be the difference between the com. If a small amount of Al(OH)3 separates. 16.1306 0. Repeat the ignition to gravimetric method should be used when a recovery of constant weight avoiding any hydration or carbonation of the aluminum is indicated or when a determination of strontium by lime. NOTE 22—Hot solutions should be avoided when washing the CaC2O4 15. The Cool in a desiccator and weigh as CaO.0396 0. NH4OH till the color of indicator changes to yellow. 16. Any for determining precision prescribed in Practice E691: precipitate that separates out is assumed to be Al(OH)3 and Test Methods Practice E691 after ignition to Al2O3 this amount is added to the mass of C25 Minimum Al2O3 calculated in 16. One litre of cold 0. Wash accordance with Sections 5.2 Procedure—Subtract the percent Fe2O3 obtained in for a minimum of 1 h. %.2 Place the wet filter and precipitate in a platinum Al2 O 3 . ignited.9252 0.0141 0.2025 0.5 Calculation—Calculate the percent calcium oxide 16. if available. and filter using a retentive paper. When cooled to room temperature the supersaturated solution 14. SR and R. 45 g of ammonium oxalate (NH4C2O4) in 1 L of hot water. that escaped precipitation before may be recovered at this point nations in this study does not meet the minimum requirements by the addition of a small amount of NH4OH and boiling. To the S-1144 0. Calcium is precipitated a second time Laboratories 2 6 Materials 5 4 as the oxalate.1. In special cases where P2O5 and TiO2 need to filtrate for the magnesium determination. a correction for these oxides must be made. 15. combined oxides (See Section 5. gravimetric analysis is required.1767 hydroxide precipitation and heat the solution to boiling. and char the paper without inflaming at low heat.2.4. dissolve the ignited oxide in 50 mL B = Fe2O3.5870 boiling solution. Combine the filtrate and washing with the ones reserved from the first precipitation.2 from the percent the paper and precipitate with five 10-mL portions of cold.3. and redissolved with HCl. and retain for the 16. for the purpose of this test stirring continuously until the methyl red just turns yellow.2.2096 0.1 Add 30 mL of HCl (1 + 1) and 20 mL of 10 % oxalic S-1145 0.2 The user is cautioned to verify by the use of reference 16. and weighed as CaO. the calcium oxide in the covered platinum crucible at 1000 °C. Sr and r.6.1 Scope—Aluminum oxide.0480 0.2 The following precision statements are provisional. this to the mass of Al2O3 determined in 15. Aluminum Oxide hydroxide still more slowly (dropwise. % 5 ~ M/W ! 3 100 (9) Copyright by ASTM Int'l (all rights reserved). and wash as in 16. tate is converted to CaO by ignition and weighed. 3. Add 40 to 42 mL of the obtained. Finish the titration by adding the (5 + 95) freshly boiled for 10 to 15 min and cooled to 27 6 3 KMnO4 standard solution dropwise until the end point is again °C.1 Scope—This volumetric test method is used mostly for acid to the combined filtrates from the iron and aluminum ordinary control work in the plant laboratory. that the bias of this test method is 0. At this point.4.1.3. Traces of strontium. N): 17.4.1 Two laboratories cooperated in testing on four lime. W = mass of standard sodium oxalate. 17. basis.4 Procedure: 17.1. Thu Jun 8 19:00:12 EDT 2017 12 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. Filter through purified asbestos or a wad of glass wool. where: stone samples and obtained the precision data summarized in F = CaO equivalent of the KMnO4 solution in grams Table 3.5 to 1 mL dropwise. stirring continuously until the methyl red just turns yellow. W = original mass of sample. Calcium Oxide by Volumetric Method 17.06701 = sodium oxalate equivalent to 1 mL of 1 N limestone samples and obtained the precision data summarized KMnO4 solution. wash the precipitate from the 17.06701 (10) V = KMnO4 solution used in titration.6. add the ammonium magnesium. g. the Remove from the heat and let stand until the precipitate has calcium oxalate precipitate is dissolved with dilute sulfuric settled and the supernatant liquid is clear.3. or oxalate that may be present will also be titrated hydroxide still more slowly (dropwise. Drop the folded filter paper that (Na2C2O4) or equivalent as follows: contained the original precipitate into the liquid and macerate 17.3 Titrate with 0.6.1.2 The user is cautioned to verify by the use of reference N = normality of KMnO4 solution. a precipitate begins to form.3.1. % 5 ~ V 3 F ! /W 3 100 (12) where: N 5 W/V 3 0. Add to the contents of the beaker 250 mL of hot. cover and allow to age for several days.02804 = CaO equivalent to 1 mL of 1 N KMnO4 solution.3.5 Calculation—Calculate the percentage of CaO in the ized before the next one is added. standardize against the National Institute of Standards and 17. Fold (KMnO4) in 1 L of water and boil gently for 20 to 30 min.1 Two laboratories cooperated in testing on twelve 0. 17.4.175 N KMnO4 solution until the pink Technology’s standard sample 40C of sodium oxalate end point is obtained. add ammonium hydroxide (1 + 3) slowly until free of interfering elements. Standard Solution (0.1 Add 30 mL of HCl (1 + 1) and 20 mL of 10 % oxalic 17. The calcium equivalent of the oxalic the total washings to 125 mL (See Note 23). g. adequate for the contemplated use. with a pipet) while and calculated as calcium on an equivalence. g. Allow to cool and acid and the liberated oxalic acid is titrated with standard filter at the end of 1 h.175 the CaC2O4 precipitate. g. barium. 17. especially with those products that are boiling solution. No further reproductions authorized.3 Heat the contents of the beaker to 60 °C and titration to avoid introduction of traces of organic matter due to the action complete the titration at this temperature by adding KMnO4 of the hot sulfuric acid on the paper. sample using the CaO equivalent from 17. the paper and leave it adhering to the upper portion of the Dilute again to 1 L.1 Dissolve 5. . g. beaker. not weight.3. Add 25 mL of hot saturated ammonium oxalate while stirring. these would consume KMnO4 and solution until a slight pink color persists for 30 s. mL. Wash the paper with cold water. allowing each drop to become decolor.6 Precision and Bias: F 5 N 3 0. CaO/mL. 0.5 Determine the CaO equivalent of the KMnO4 M = mass of CaO. To the of giving exact results. limiting potassium permanganate.2 Transfer 0. in solution. in Table 3. The filter paper is not introduced at the beginning of the 17.1 Potassium Permanganate. mL. and N = normality of KMnO4 solution. for magnesium. 16.3. and materials. and 17.02804 (11) 16.5 g of the standard sodium oxalate dried it with a stirring rod. Stir until the oxalate has dissolved. 17.6.2). where: F = CaO equivalent of KMnO4. C25 − 11´2 where: 17. and diluted H2SO4 (1 + 19) and heat to 80 to 90 °C. Copyright by ASTM Int'l (all rights reserved).2 With a jet of hot water. if available. standard KMnO4 solution at the rate of 25 to 35 mL/min. Add 250 mL of diluted H2SO4 discharged (See Note 24).1.2 Summary of Test Method—In this test method. Add the last give high results for CaO.6 Precision and Bias: V = KMnO4 used to titrate sodium oxalate. Retain the filtrate acid is determined and the grams of CaO calculated. 17.64 g of potassium permanganate paper into the beaker in which the precipitation was made. the pink color of the solution will be at 105 °C to a 400-mL beaker. but it is capable hydroxide precipitation and heat the solution to boiling. and solution as follows: W = mass of sample. while stirring slowly.1.3 Special Solutions: NOTE 23—A Gooch crucible may be used instead of filter paper to filter 17. Let stand until the pink color disappears (about NOTE 24—There will always be some fine particles of precipitate imbedded in the pores of the filter paper which are dissolved by the acid 60 s) (See Note X1.4 Determine the exact normality of the KMnO4 solution from the following: CaO. 16.5 as follows: 17. Reduction of the phosphate precipi.3 Special Solutions: 19.2 and 19. the manganese content of the pyrophosphate residue should be determined 19. CO2. then add and weigh accurately to within 0. Pre-ignite in a muffle furnace at approximately 400 ammonium hydroxide wash solution (5 + 95). g. g.1 Fifteen laboratories cooperated in testing on three tures. 19.1 Add 2 drops of methyl red indicator to the combined 19.2 = molecular ratio of 2MgO to Mg2P2O7 × 100. No further reproductions authorized. The difference Dilute the solution to 100 mL. g.4 Calculation—Calculate LOI as follows: 18. The MgO equivalent is then calculated. 0.3. Loss on Ignition 18.4. and cool the solution 19.S. place paper and where: precipitate in a weighed platinum or porcelain crucible. magne.5. If filtration was through paper. 18. (Mg2P2O7). if available. The loss in weight is due to a release of free moisture. Slowly A = mass of crucible + sample. Dilute 50 mL of NH4OH with 950 mL of water and add 1 or 2 chemically combined “lattice” or “hydroxy” water. precision data summarized in Table 3. place directly in a muffle at 400 °C and raise heat to 1100 °C.1 Scope—Magnesium oxide in lime and limestone may 36. cool in desiccator.2 Ammonium Hydroxide Wash Solution (5 + 95)— weight.2/B (13) materials. Dibasic Solution (250 g/L)— 19. There is also a danger of occluding carbon in the samples of high calcium limestone to obtain the precision data precipitate if ignition is too rapid. % 5 A 3 36. mL of the (NH4)2HPO4 solution. g. SO2. quicklime for several more minutes.463 % LOI.1 Four laboratories cooperated in testing on three gravimetric method has been used successfully throughout the limestone samples and three laboratories cooperated in testing industry to determine magnesium within this wide range. cool to room temperature.5. and maintain at this temperature for a minimum of and wash the filter paper well with hot diluted HCl (1 + 99).5 Calculation—Calculate the percentage of MgO to the 19.6.2 The user is cautioned to verify by the use of reference MgO. Also. mL of HNO3. 20 min or until constant mass is obtained. Copyright by ASTM Int'l (all rights reserved). and 18.01 % as follows: materials. washing with diluted NH4OH (5 + 95). Precipitate the represents the loss on ignition. and resulting carbon (Warning—Extreme caution should be exer. C25 − 11´2 17. ing the weighed sample is ignited to constant weight. the crucible cover is not required.4 The user is cautioned to verify by the use of reference nearest 0. standard sieve to a constantly until the solution is alkaline or the crystalline tare-weighed porcelain or platinum crucible. on an additional nine limestone samples thereby obtaining the 18.6 Precision and Bias: much as 22 % for dolomitic limestone.2 The user is cautioned to verify by the use of reference phate from the filtrate after removal of calcium. 18.5. 19. The loss and concentrate to about 250 mL.4 Procedure: may be present. if available.1 Scope—Loss on ignition (LOI) is the loss in weight Dissolve 250 g of dibasic ammonium phosphate expressed as percent of the initial “as received” sample weight ((NH4)2HPO4) in 1 L of water.3. sium is doubly precipitated as magnesium ammonium phos.5. 18. cised during this ignition. Ignite at 1100 °C for 1⁄2 h. Thu Jun 8 19:00:12 EDT 2017 13 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. g. 18. When testing about 15 to 20 mL of NH4OH in excess and continue stirring quicklime.4. magnesium ammonium phosphate as before and allow to stand for about 2 h in a cool place. 19.3 Procedure—Transfer approximately 1 g of the sample to room temperature. °C for 30 min.3 The reproducibility (Practice E691 [R]) was found to and deducted as Mn2P2O7.5. Add NH4OH slowly while stirring prepared to pass a 100-mesh (149-µm) U.5. The precipitate materials.1 mg. if available. be 0. char the paper without inflaming and carefully burn off the B = mass of crucible plus sample after ignition. and between the original mass of the sample and the final mass add 1 mL of the 20 % solution of (NH4)2HPO4. vary from a few tenths to 2 % for high-calcium limestone to as 18.).2 Summary of Test Method—The tared crucible contain- filtrates from the determination of calcium. and volatile pyrolytic products of any organic material that 18. The pyrophosphate 18.6.3 Filter the precipitate on paper or in a tared Gooch crucible. Magnesium Oxide B = sample. that the bias of this test method is where: adequate for the contemplated use. and weigh as Mg2P2O7 (See Note 25).2 The repeatability (Practice E691 [r]) was found to be NOTE 25—For research purposes or in the most exacting types of work.2 Dissolve the precipitate with hot diluted HCl (1 + 9) °C 6 20 °C. obtained after ignition of the sample at 1000 °C to constant 18.1 Ammonium Phosphate. A = Mg2P2O7.6.2 Summary of Test Method—In this test method. Filter and wash with cold dilute preignition. 18. Allow the beaker and precipitate to may be placed directly into a muffle at 1000 °C avoiding stand in a cool place overnight.4. C = mass of sample. . that the bias of this test method is adequate for the contemplated use. If filtered LOI. Cover with a lid magnesium ammonium phosphate begins to form. 250 g/L.158 % LOI. 19. acidify with HCl. Then increase muffle temperature to 1000 18. Add to this solution about 10 in weight is the LOI of the sample.3. that the bias of this test method is is ignited and weighed as magnesium pyrophosphate adequate for the contemplated use. % 5 ~ A 2 B ! /C 3 100 (14) through a Gooch. for percent LOI given in 19.5 Precision and Bias (Limestone): tate can result if carbon is in contact with it at high tempera. quency than the 95% probability limit would imply.572 0.1 Repeatability limits are listed in Table 4. weighing. R is the interval representing the critical 20. r—Two test results obtained from a sample of the material by drying to constant weight at within one laboratory shall be judged not equivalent if they a temperature slightly above the boiling point of water.883 Do Lime #2 2. SR Hi-Cal Lime # 1 0.1 Scope—The free moisture in hydrated lime is that method. glass-stoppered.8 The precision statement was determined through sta.2 Repeatability Limit.190 0. 20. 19. concerns the platinum crucible data.4 The terms repeatability limit and reproducibility limit counterpoise carried through all the operations is a desirable are used as specified in Practice E177.4 Procedure—Weigh 1 g of the prepared sample in the difference between two test results for the same material.3 Reproducibility Limit.2 Summary of Test Method—The sample in a container is the same material.278 0. Quickly stopper.275 0. Free 2 moisture. a desiccator.056 0. and the associated probability of 95% as only method have not been determined.6 Precision and Bias (Lime): Hi-Cal Lime # 1: High Calcium Lime 19. over the sample in a container placed inside a 115 to 120 °C TABLE 4 Loss on Ignition Results for Lime Using Platinum.5 Calculation—Calculate the percent “free moisture” as tained in this ILS must not be treated as exact mathematical follows: quantities which are applicable to all circumstances and uses. 20. large porcelain crucible. the details are given in RR:C07-1008.2 weight represents “free moisture” loss at 120 °C. cool in different laboratories. The use of a similar weighing bottle as a 19.7 Bias—At the time of the study. lifting the stopper momentarily just 19. or judged not equivalent if they differ by more than the R value wide-form.1 The precision of this test method is based on an Hi-Cal Lime #2: High Calcium Lime Do Lime #2: Dolomitic Lime interlaboratory study conducted in 2008. R—Two test results shall be 20.6.748 0.204 0.6 Precision and Bias—The precision and bias of this test general guides. therefore no statement on bias is being made. r Limit.6. 19. Remove the stopper and heat in a obtained by different operators using different equipment in drying oven at 115 to 120 °C for 2 h. the con- Except for the number of reporting laboratories in some cases. The same equipment on the same day in the same laboratory.3.316 Hi-Cal Lime #2 2. 20. that is. Up to ten laboratories Do Lime #1: Dolomitic Lime tested a total of four alloys in three types of crucibles. for that material.2 Summary of Test Method—Free moisture in hydrated 7 Supporting data have been filed at ASTM International Headquarters and may lime is determined by aspirating a slow stream of CO2-free air be obtained by requesting Research Report RR:C07-1008.6. B = mass of crucible and sample after heating at 120 °C. Thu Jun 8 19:00:12 EDT 2017 14 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. Free Moisture in Hydrated Lime reference material suitable for determining the bias for this test 21.6. ventional definition of “hygroscopic moisture” or “free water” Practice E691 was followed for the design and analysis of the (also known as “free-moisture”) is accepted. Copyright by ASTM Int'l (all rights reserved). should be considered 20.6.3 Special Apparatus: 19. the amount data. 21. C25 − 11´2 19.6.532 0. differ by more than the r value for that material. on chemically bound to the lime and which cannot be liberated four materials which are described below: except at higher temperatures. . Each labo. This distinguishes it from the hydroxyl water that is tistical examination of 252 results.460 0. procedure unless a single pan balance is used.5 Any judgment in accordance with statements 19.096 0.3.113 0.779 Do Lime #1 0. No further reproductions authorized. g. arise.158 0.2.1 Reproducibility limits are listed in Table 4.1 Scope—For the purpose of this test method.6. and weigh.3 would normally have an approximate 95% prob- ability of being correct. water that is released from the sample at a temperature of 115 19. Every test result represents an individual determination. sometimes with considerably greater or smaller fre. B The average of the laboratories’ calculated averages. and 19.270 0. The loss in 19.440 A Statistics based on results from 10 laboratories. r is the interval representing the critical difference between two test results for 20.157 0. x̄B Repeatability Reproducibility Repeatability Reproducibility Standard Standard Limit.1 Bottle. low-form. R Deviation. loss in weight represents the free moisture. % 5 ~ A 2 B ! /C 3 100 (15) The limited number of laboratories reporting replicate results using the platinum crucibles guarantees that there will be times where: when differences greater than predicted by the ILS results will A = mass of crucible and sample before heating. obtained by the same operator using the heated in a drying oven at 115 to 120 °C constant weight. 20. Free Moisture in Limestone ratory reported up to three replicate test results for the analysis. and Quartz Crucibles Combined (%)A Material Average. Sr Deviation. before weighing.6. at least as C = original mass of sample. Porcelain. there was no accepted 21. g. The and repeatability limit and the reproducibility limit. from ten laboratories. however the precision statistics ob. g.7 of water and any other volatile matter than can be expelled 19.315 0.6. stoppered weighing bottle.796 0. a rough indicator of what can be expected. to 120 °C. 21.6 Precision and Bias—The precision and bias of this test 21. following order starting from the air source: 21. g. Fleming. Connect the sample bottle to the purifying train by means of flexible tubing and pass a slow current of dry 22. shall consist of A = mass of sample flask + sample.3. a series of scrubbers and absorption bulbs to remove CO2 and B = mass of sample flask after drying.3. C Fleming jar containing sulfuric acid to remove water from air.1.3. remove it to the balance case for several 22. exchange stoppers. . 21. C25 − 11´2 oven.3. 21.3. % 5 ~ A 2 B ! /C 3 100 (16) tubes for conducting the dry air over the sample. U-shaped with side arms and glass minutes before weighing it.1. No further reproductions authorized. “free moisture” loss as 120 °C.2 Bottle B. E 50-mL sample flask. the sample as follows: 21. F Drying oven operating at 110 °C. Contains stopper slightly for an instant to relieve any vacuum that may Anhydrone on left side and Ascarite on right side.3. remove it from the oven with following: another quick exchange of stoppers. located outside the oven where: F for conducting the dry air over the samples. 1 Apparatus for Free Moisture in Hydrated Lime Copyright by ASTM Int'l (all rights reserved). transfer with Ascarite.2. The loss in weight of the sample is equal to the free exist in the bottle. Samples of lime and hydrated lime are analyzed for CO2 to 21.1 Sample Flask E. containing sulfuric acid to remove 22. The CO2 is absorbed and using glazed paper folded in the shape of a funnel. sium perchlorate) to complete the drying of the air. lift the stoppers.2. and moisture from the air. also filled with Anhydrone and as uncalcined limestone. G Absorption bulb filled with Anhydrone to prevent moisture backup into sample.1 Soda-Lime Tower A. a special sodium hydroxide absorbent.3. and the it rapidly into the previously weighed bottle and immediately gain in weight of the absorbtion tube is determined and restopper it.1 The flask shall be fitted with an interchangeable hollow ground-glass stopper. Carbon Dioxide by Standard Method soda lime is exhausted. Insert the bottle into the 120 °C oven and quickly calculated as percent CO2.5 to 3 g of the prepared sample. D Absorption bulb filled with Anhydrone (Magnesium Perchlorate) to complete drying of air. A Soda-Lime Tower at inlet to remove CO2. filled with Anhydrone (magne. The loss in weight of the sample represents moisture of the hydrated lime.3 Special Apparatus: containing the sample as a counterpoise in all weighings unless 21. containing sulfuric acid.3. determined to verify the presence of carbonates other than 21. to cool.1 The apparatus illustrated in Fig. Disconnect the 22. g. at the air inlet to remove CO2 method have not been determined. supplied with a 21. Thu Jun 8 19:00:12 EDT 2017 15 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. Use a bottle similar to the one 21. consists of a a single-pan balance is used. 21.4 Absorption Bulb D. calcium or magnesium. from the air. Side arms are shaped to hold rubber tubing. g.2 Drying Tube B. 2 consists of the sample bottle from the train. 50-mL flat-bottom.4 Procedure—Weigh 2. illustrated in Fig. 1).3.1 Purifying Jar A. check for the presence of carbonates. equipped with two glass entry Free moisture.1.3.1 Scope—Carbon dioxide in limestone is sometimes water from the air.7 Absorption Bulb G. containing lime water to show when the 22.2 Purifying Train (See Fig. most of which are there 21. FIG. These may include carbonates of iron.2. manganese. When cool.5 Calculation—Calculate the percent “free moisture” in ground glass joint and solid ground glass stopper. and place it in a desiccator 22. The apparatus are arranged in the C = mass of sample. scrubbers to remove water and sulfides.2. located on the exit side of the sample bulb as a protective 22.3.5 Sample Flask E.2. 1.2. glass-stoppered flask.3.3 Special Apparatus: CO2-free air through the apparatus for 2 h. and occasionally traces of other substances.2 Summary of Test Method—The sample is decomposed barrier against atmospheric moisture.3. and just before weighing.6 Drying Oven F. B Bottle containing lime water to show when soda lime tower is exhausted.3 Fleming Jar C.2. with HCl and the liberated CO2 is passed through a series of 21. 24/40 glass joint. A = mass of absorption bulb + CO2.5 g for limestone and 5 g for lime or hydrated lime.2 Weigh the absorption bulb and attach it to the train. (E) and. with ground-glass stopper air through the apparatus for 10 to 15 min. g. immediately above this unless a single pan balance is used. Open containing distilled water to retain most of the acid volatilized the stopcock of the separatory funnel and admit air through the from the alkalimeter. A top layer of Anhydrone about 22.3 Start cold water circulating through the condenser 22. 0. Ascarite in right side. Fleming.1 Weigh an indicated amount of prepared sample. 22. and Ascarite is then added to almost fill the bulb.5 Calculation—Calculate the percent CO2 as follows: 3⁄8 in. Used to introduce acid into flask. 250-mL.3.4 Separatory Funnel D. filled with Anhydrone in left side and Ascarite in right side.8 Gas-Washing Bottle H. Connect the sample flask to method have not been determined. with fritted disk through which passes a tube for admitting purified air. containing concentrated H2SO4. place a small hot plate or gas burner under mist that may have been carried over. containing concentrated H2SO4.4. with CO2-free air passing at a moderate rate through containing concentrated H2SO4 and trap I.3. Purge the joint. g. 250-mL. M Purifying jar.3. C25 − 11´2 A Purifying jar. bent at the end extends into the sample flask about 1⁄2 in. thick is placed on top of the Ascarite and topped off with a covering of glass wool.1. . containing Anhydrone to re- and continue the flow of purified air at about three bubbles per move last traces of water vapor. L U-guard tube with Anhydrone in left side and Ascarite in right side. and transfer to 22. Close 22. J Absorption bulb containing Anydrone. D Separatory funnel. the stopper with the interchangeable hollow ground-glass joint 22. 250-mL. H Gas-washing bottle.4 Procedure: C = mass of sample. E Condenser. No further reproductions authorized. I Trap. containing Ascarite filled the absorption bulb.3.1. disconnect it from the train and weigh. B Drying tube.12 Purifying Jar M.1. 2 Apparatus for Carbon Dioxide by Standard Method 22. containing concentrated H2SO4. place 50 mL the bottom. where: 22. F Gas-washing bottle. and 22. U-shaped. with fritted disk.10 CO2 Absorption Bulb.4. 2). top of the funnel to force the hydrochloric acid into the 22.4. Anhydrone in left side. Thu Jun 8 19:00:12 EDT 2017 16 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.6 Precision and Bias—The precision and bias of this test the 250-mL Erlenmeyer flask. containing water to retain most of the acid volatilized from the alkalimeter. 24/40 ground-glass apparatus as shown in the diagram (See Fig. last traces of HCl.1. place a layer of glass opening the stopper momentarily to equalize the pressure.1.1. from Remove the glass stopper from separatory funnel. Copyright by ASTM Int'l (all rights reserved). 22.3.3. Remove the hot plate 22. Fleming. to remove any SO3 the absorption train. g. containing mossy zinc to remove the Erlenmeyer flask (C). C Erlenmeyer flask. system free of carbon dioxide by passing a current of CO2-free 22. is placed another layer of glass wool. as follows: On the bottom of the bulb. FIG.11 U-Guard Tube L. containing H2SO4. CO2 .1. B = mass of absorption bulb before the run. 250-mL.9 Absorption Bulb J. 250-mL with fritted disk.5 Condenser E. and interchangeable hollow ground-glass joint. second for 30 min to sweep the apparatus free of CO2.7 U-Tube G.6 Gas-Washing Bottle F.3.3.3. of dilute HCl (1 + 1) in the separatory funnel (D) and replace 22. Use wool extending above the bottom outlet and on top of this a a second absorption bulb as counterpoise in all weighings layer of Anhydrone about 3⁄8 in. % 5 ~ A 2 B ! /C 3 100 (17) 22. thick.1.3 Erlenmeyer Flask C.3. Fleming. 250-mL with fritted disk. A delivery tube 22. K CO2 absorption bulb containing Ascarite. G U-tube containing mossy zinc to remove the last traces of HCl.1.1. the sample flask and boil for about 2 min. usually as pyrite. that are soluble in dilute HCl. and contents in a weighed platinum crucible and slowly char the 0.00 Expected S Range. samples of limestone and lime materials covering the range 24.00 2. H2S or not react at all with the acid. add 5 mL of HCl (1 + 1).1 Scope—This test method will determine sulfur adequate for the contemplated use. g.001 as follows: 23.50 suspension.500 10.1 Six laboratories cooperated in testing on four BaSO4. add 10 mL of hot BaCl2 solution.2 Summary of Test Method—In this test method. Cool. flaming. the difference can be assumed to be present as with barium chloride (BaCl2) and the SO3 equivalent is iron disulfide. g 24. % 5 A 3 13. and add water for this sintering.271 % SO3 per weight in grams of sample analyzed).6. precipitate is well formed. compounds.2 and 23. The solution is made ammoniacal and the 23.3.2 Summary of Test Method—The sample is fused with 23. 24. paper without flaming. Allow to stand overnight.343/W 3 100 (18) about 250 mL. adjust the volume to SO3 .001 as follows: To the filtrate add 5 mL of HCl (1 + 1).3 The reproducibility (Practice E173 R2) was found to be (0. and bring the solution to boiling. place the crucible and cover to boiling.4 Calculation—Calculate the percentage of sulfur to the from 0. Add 50 mL of diluted HCl (1 + 1) and heat until 1.500 to 2. filter using a retentive paper and wash with hot water. The 23.20 10.00 1. and allow to stand Remove the crucible and wash with hot water.3. Filter through a medium-textured paper and wash in a 400-mL beaker.00 to 5.1 Scope—Sulfur in limestone is chiefly.2 The repeatability (Practice E173 R1) was found to be S. Total Sulfur by Sodium Carbonate Fusion will not be included because they will either be volatilized as 24. mostly present as sulfates in lime and limestone.3. Cool in a desiccator and weigh as 23. A = mass of BaSO4. 23. (See Note 26). overnight at room temperature.73/W (19) (0. Burn off the carbon and ignite in a 23. Place the paper and contents in NOTE 27—It has been found that 10 mL of 30 % hydrogen peroxide a weighed platinum crucible. heat to boiling. with the following: 24. Heat the solution to 23.6. that the bias of this test method is 23.343 = molecular ratio of SO3 to BaSO4. where: 23. precipitated with a 10 % solution of barium chloride.001 to 0.001 to 0.4 The user is cautioned to verify by the use of reference materials. Digest Add the indicated amount of Na2CO3 and mix well. g.00 the reaction has stopped and decomposition is complete. cool in a desiccator. paper and wash the precipitate with hot water.50 5. Burn off all the carbon. Increase the heat 50 °C every 15 few drops of methyl red indicator and render the solution min until 1000 °C is reached and maintain at this temperature alkaline (yellow color) with NH4OH (1 + 1). the air entering the crucible after the bulk of the carbon dioxide purpose if necessary. % Sample Weight. Add a a muffle at 600 °C for 15 min.2 Add a few drops of methyl red indicator and render the solution alkaline with NH4OH (1 + 1).15 % SO3 to obtain the precision data given in nearest 0. and weigh. ignite in a muffle at 1000 °C. if available.6. To the boiling solution. Boil 10 mL of hot BaCl2 solution. Sulfur Trioxide 23. Filter through a retentive A = mass of BaSO4. Place paper and W = mass of sample. g 0. and cover with hot water. Take care to keep the volume of NOTE 26—Since not enough flux is used to produce more than a solution between 225 and 250 mL.6.6. g. Filter through a retentive paper and wash has been released effects very speedy oxidation in the porous mass. Add 10 mL the residue thoroughly with hot water. Heat the solution for 15 min.00 5. the precipitate with hot water.00 2.00 5. No further reproductions authorized. % Sample Weight.6. % 5 A 3 0.00 lain crucible in accordance with the following: 2.3 Special Solution: sodium carbonate and the ignited mass is leached in water and dissolved with HCl.50 to 12.00 0. . Continue the boiling until the until solution is complete and all bromine has been expelled.135 % SO3 per weight in grams of sample analyzed). calculated.5 Calculation—Calculate the percentage of SO3 to the boiling. 24.04 to 5.1 Barium Chloride Solution (100 g/L)—Dissolve 100 hydroxide precipitate is filtered. Copyright by ASTM Int'l (all rights reserved). Dilute the filtrate to 250 bromine water (See Note 27) and then add sufficient HCl mL.200 to 1. nearest 0. stir well. Heat in for several minutes at a temperature just below boiling. slowly and with where: stirring. present as sulfide. Thu Jun 8 19:00:12 EDT 2017 17 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. g Na2CO3 Weight. sulfate in the following test method is in excess of that present as is precipitated from an acid solution of the lime or limestone soluble sulfate.4 Procedure—Select and weigh the prepared sample into precipitate is ignited and weighed as barium sulfate (BaSO4) a 250-mL beaker containing 50 mL of cold water in accordance and the SO3 equivalent is calculated. if not wholly. The sulfur in the filtrate is g of barium chloride (BaCl2 · 2H2O) in 1 L of water. and slowly char the paper without (H2O2) may be substituted for the bromine water to accomplish oxidation without affecting the analytical result.00 Stir until all lumps are broken and the lighter particles are in 0. and add slowly (1 + 1) to make the solution slightly acid to methyl red.3 Procedure: Expected SO3 Range.1 Select and weigh the prepared sample into a porce- 0.3. If the total sulfur obtained 23.6 Precision and Bias: muffle at 1000 °C for 1 h. Iron pyrites and other sulfides 24. C25 − 11´2 23.5 2. 1 Scope—This test method covers the determination of 25.5.7. 24. Thu Jun 8 19:00:12 EDT 2017 18 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.1 It has been found through round robin studies that the 25. in to consume oxygen.1 Copper (Low-Sulfur) Ring Accelerator. Method 25.) form or sample matrix.3. 25. may be standardized daily by running limestone complete absorption of SO2 in a small volume of solution. de. stir until the KI is dissolved. blue color when titrating. Total Sulfur Method.8 Loading Funnel—Three-legged funnel that fits over 25.3. The Leco instrument. tion valve to provide an even and adequate flow of oxygen 25. g.4. standard solutions.7 Procedure: through a purifying train consisting of a sulfuric acid tower. The lime- mately 10 mL in capacity marked with 200 divisions. Section 24. assembly and titrator to warm up.6. apparatus and for day-to-day variation in the percentage of 25. 25.3 Tin Metal (Low-Sulfur) Accelerator.5 Precision and Bias: 25. Slowly add 25. scribed in 25. (For temperature of approximately 1650 °C. Copyright by ASTM Int'l (all rights reserved). have adequate capacity and may be provided with suitable 24.73 = mass of molecular ratio of S to BaSO4 × 100. No further reproductions authorized.094 % S per weight in grams of sample analyzed).3.3.6 Calibration—This test method and instrument should an absorption and titration vessel of appropriate volume and be standardized by using a limestone sample of known sulfur contain an inlet bubbler tube for the sulfur gases with a float content as determined by the Total Sulfur Method by Sodium valve to prevent backflow of liquid when the sample is starting Carbonate Fusion. sulfur in concentration from 0. recovery of sulfur. C25 − 11´2 W = sample.5 Special Solutions: ture of a high-frequency induction furnace. Add 6 g of potassium reduction coil that will avoid heating some types of samples iodide (KI). and another absorption bulb containing 13.5. sulfur in various types of lime and limestone samples is 25. The train of NOTE 28—Discard any starch solution that imparts a red tinge to the the induction furnace shall include an oxygen purifier. combustion.6 Starch.5.1.2 The repeatability (Practice E173 R1) was found to be covers. and nated with NaOH.5. .1 KIO3 Standard Solution A—Dissolve 0.3. Compensation is also made for the starch (for example.500-g sample. During the 25. 25. The vessel must be shaped to effect addition. the use of of the sulfur in the sample will take place regardless of sulfur iron powder is recommended because of its low blank.4 The user is cautioned to verify by the use of reference 25. granular. an 25.3.7 Timer.3.3. the SO2 is absorbed in an acidified starch-iodine 25.5.4. The crucibles for use in the induction furnace must in 24. soluble. 24.1 Allow 15 min for the electronics in the furnace absorption bulb containing 20 to 30-mesh inert base impreg.2 Iron (Low-Sulfur) Accelerator—Iron chips. the presence of an operator. 25. millilitres of water.5 Glass Accelerator Scoop. if available.5.2 Starch-Iodide Solution—Transfer 2 g of soluble sulfur recovered as SO2. Arrowroot) to a 50-mL beaker. The latter is KIO3 in 900 mL of water containing 1 g sodium hydroxide standardized against limestone standard samples of known (NaOH) and dilute to 1 L. ranges from 0.1 Induction Furnace—The induction furnace shall be NaOH and continue stirring the solution until the appearance supplied with a rheostat used to control the power input to the changes from cloudy to translucent.5 Potassium Iodide (KI) Crystal. as determined by the titrator comes equipped with a buret that should be approxi. converted to oxides of sulfur. add a few blank due to accelerators and crucibles. and stir into a smooth paste. resets. 25.3. dispensing a few millilitres of starch solution at a time. Total Sulfur by the Combustion-Iodate Titration the crucible and simplifies addition of sample. 24. The stone standards are run to determine the day-to-day variations automatic titrator utilizes a photoelectric cell to activate a in the test method and to verify that the electronics in the Leco titrator inlet valve that allows the titration to proceed without are working properly. 25. that the bias of this test method is Turns off the furnace at end of preset time and automatically adequate for the contemplated use. primarily sulfur dioxide (SO2). and dilute to 1 L.021 to 2.02 to 0.1 Potassium Iodate.4 Combustion Crucibles—The crucibles for use with 24.1.2 Summary of Test Method—A major portion of the 25. 25. (0.1 Six laboratories cooperated in testing on four the induction furnace must be of adequate thickness to retain samples of limestone and lime materials covering the range the molten slag and have a sulfur blank as low and consistent from 0.6 Starch Dispenser—A plastic bottle with a device for be (0.3 The reproducibility (Practice E173 R2) was found to 25.4. At the combustion 25.5.005 to 1 %.15 % sulfur to obtain the precision data given as possible.05 %.3.3 Oxygen Purifiers—Reagent-grade oxygen from a practice of pre-igniting samples at 1000 °C causes erratic commercial tank is passed through a suitable two-stage reduc.065 % S per weight in grams of sample analyzed). This practice should not be used.2227 g solution and titrated with potassium iodate.4. materials.3.2 Automatic Titrator—This apparatus shall consist of 25. the buret reads sulfur content to compensate for characteristics of a given directly in percent sulfur. by combustion in a stream of oxygen at the elevated tempera- 25.5.2 and 24. complete combustion samples containing very low percentages of sulfur.4 Potassium Iodate (KIO3) Crystal. anhydrous magnesium perchlorate Mg (ClO4).4 Reagents: 25. having a 0 to 15-min range in 1⁄4-min intervals. too rapidly during the early stages of combustion.4.4. Add 4 g of 25.5.3 Apparatus: starch to 500 mL of distilled water while stirring. For a 0. A flowmeter precedes the induction furnace assembly. The reference materials whose sulfur content. The correct W = weight of sample.9. materials.4 The user is cautioned to verify by the use of reference same level.9. Phosphorus by Molybdovanadate Method 25. Thu Jun 8 19:00:12 EDT 2017 19 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. 26.8.3. tometrically.7. and copper ring have been found to be suitable B = buret reading for Blank determination. 25. as each furnace will burn differently in accordance with type and amount used.2 The repeatability (Practice E691 [r]) was found to be into position in the combustion tube.7. Sulfur % Sample Weight (g) 0.12 Inspect the crucible for a proper burn.0120 % sulfur. C25 − 11´2 25.7.2 Set the grid-current tap switch to low. with the recovery and may be helped by a slight change in accelerator sample and accelerators that will give a complete combustion amounts.3. Slowly rotate the end-point control 26.7.001 0. the unit will begin solution to form the heteropoly phosphomolybdovanadate titrating automatically. at approximately 400 mA as indicated on the plate current 25.7. Total phosphate is determined after a strong 25.7. and indicate a reading of at least 400 mA before complete com. Both conditions indicate poor sulfur high position. iron chip.3 Set the automatic timer to the estimated time re- R quired to evolve the sulfur in the sample completely.2 and 25. that the bias of this test method is 25. .3 Special Solutions: bumpy surface or appearance of non-combustion indicates that 26. g. 25.10 Turn on the power of the high-frequency furnace.7.1 Phosphorous Standard Stock Solution (0. Fill the iodate buret.4 Weigh the sample and brush carefully into the reference material. After the indicator light (for samples. oxidation decomposition with perchloric acid. and combustion crucible using the loading funnel. Porous covers should be used to prevent splattering F = furnace factor.8 With the oxygen flow at 1 L/min.8 Calculation: ammeter. for % sulfur given in 25.7 Place the crucible and sample on the pedestal and lift 25. place the switch in the in its ortho form will combine with ammonium molybdovana- neutral position and fill the KIO3 buret again.5 mg the furnace temperature was too low. 25.500 A2B 25. dovanadate which is then added reacts with the phosphorous in 25. No further reproductions authorized. 0.0983 g of potassium dihyrogen phosphate.11 As sulfur dioxide is given off. g. Always fill to the 25. 26.7. Min where: Quicklime 8 A = buret reading as % Sulfur (S). A rough. Hydrated Lime 10 Limestone 12 B = buret reading for Blank determination.9. and add the HCl to the middle of the be 0.1 Nine laboratories cooperated in testing on three sulfur determinations) using a crucible that contains all the samples of high-calcium limestone to obtain the precision data accelerators but no sample.1 Scope—This method is suitable for the determination in a clockwise direction until it has added KIO3 in the amount of small amounts of phosphorous in lime and limestone to give a solid medium blue color. vessel. as F5 (20) ~A 2 B!/~W 3 2! follows: Sample Time. The absorbance of the solution is measured with a indicator light stops blinking for a period of time.3 The reproducibility (Practice E691 [R]) was found to bottom of titration vessel.9.9 Precision and Bias: 25.8.7. Sticking of the porous P/mL)—Weigh 1.6 Run a blank determination before each series (of 25. close stopcock on 25.7. the insoluble residue fused with Na2CO3. The titration is finished when the complex.2 Calculate the percentage of sulfur in the sample by the sample as follows: using furnace factor F. bell-shaped portion of the titration vessel. the solution filtered. Ammonium molyb- bustion of sulfur can take place. sample weight is determined by the estimated sulfur content of 25. if available. into a 250-mL beaker and dampen with about 5 to 10 Copyright by ASTM Int'l (all rights reserved).1 Calculation of Furnace Factor (F) 25. The procedure is based on the fact that phosphorous solenoid valve) has stopped blinking.9. and of the hot flux and damage to the combustion tube.9. or have been too hot. The temperature will rise in the crucible as indicated by the 26. the greater the furnace temperature. Determine the position on a test run.9 Turn the double throw switch on the titrator to the end-point position (down). A = buret reading as % Sulfur (S). larly treated.2 Summary of Test Method—The sample is decomposed plate current ammeter on the induction furnace that must with perchloric acid. materials. Tin metal. Turn the switch date to yield a yellow color that can be measured spectropho- to the titrate position.7. iron powder. SiO2 expelled. cover to the crucible indicates that the furnace temperature may KH2PO4. Generally. the more accelerator where: used.5 The choice of accelerators is left to the discretion of %S5F3 (21) W 32 the user.8. 25. or the iodate photometer at 430 nm and compared against standards simi- in the buret stops falling over a period of time. Do not W = weight of sample. R = % Sulfur (by Sodium Carbonate Fusion Method) of the 25.1 Add one measure of starch solution to the titration adequate for the contemplated use. re-use crucibles or covers.0070 % sulfur. 25.7. medium. add 5 mL H2O 27. 10.70 mg of phosphorous. The prepared standard solutions will contain 0 (blank).5. heat on hot plate.4 Preparation of Standard Curve: mined from calibration curve. Cover and boil until the solution is colorless or slightly 26.7 Precision and Bias: 0.0 g of prepared sample into a 250-mL Precision Statement for % P2O5 Color beaker and dampen with about 5 to 10 mL of water.0019 0. Prepare a calibration cessed which does meet the requirements of Practice E691.3. The acid solution is oxidized to higher temperature until ash is white.0.0040 0. C25 − 11´2 mL of water.4.1 Dissolve 1. <3 %.1 Weigh 5.10.0010 0. add 2 drops of permanganate by potassium periodate. 27.0. 2. perchlorate salts to prevent small explosions from occurring in the crucible when the filter paper is charred and ignited. and 0.0031 0. dilute to volume.50. and Material Average Sr SR r R S-1145 0. Reserve filtrate. 0. HClO4.1 To each of seven individual 50 mL volumetric flasks. the use of 27. working standard solution corresponding to 0. has been determined for the 26. W 3 104 26. 1. and again used to convert manganous into permanganate ion whose color evaporate to dryness. 26.5 g of Na2CO3.5. Add 10 mL Test Method: HNO3 and 25 mL HClO4 (See Note 29). periodate is the oxidizing agent perchloric may be omitted.2 into solution 26. add 10 mL HNO3 and evaporate to dryness. dryness and heat in a muffle at 1000 °C for 2 min (See Note 31). 26.0221 0. 4. 6. additional data will be obtained and pro- blank standard as the reference solution. Copyright by ASTM Int'l (all rights reserved). 0. and mix.0063 0. and 14. Instead.3 Pipet 25 mL of solution into a 50 mL-volumetric yellow (10 to 15 min).3. SR and R. Compare against a set of Dilute 50 mL of stock solution 26. in the spectrophotometer at a wavelength of 430 nm using the Within five years.0215 0. 2.6.0 micrograms (µg) P/mL.4.3.0046 evaporate to heavy fumes of HClO4.1 Precision.0. measure the absorbance at 430 nm using the blank standard 26.1.1 Scope—In this method.25 g of ammonium metavanadate in 400 mL of 1 + 1 nitric acid in a 1 L volumetric flask.0053 0.3. Fuse residue with 0. Sr and r. . Filter through retentive filter S-1144 0. 10.0147 0. filter.2 Summary of Test Method—The same sample solution prepared in the determinations of phosphorous by molybdova- 26. Combine the filtrates 27. No further reproductions authorized. cool. 4.0175 0.0500 g pure manganese (Mn) metal in 20 mL mix.0029 0. for determining precision prescribed in Practice E691: swirling the contents of the flask during the addition. C = concentration of P in sample solution. Photometric measure- H2SO4 (1 + 1) and 10 to 15 mL HF. 26. 0. Store in a Pyrex or plastic bottle with screw cap.0144 0. curve by plotting absorbance versus concentration of phospho- 26.3. characterized by repeatability. and dilute to volume with distilled water.2) can be used for the determination heat gently with a low flame until paper chars. Allow to stand 30 min and borosilicate or plastic bottle with a screw cap. etc.0014 0. Add 10 mL of the molybdovanadate solution.1 to 26. and evaporate to heavy fumes of omitted if the SiO2 in the sample is low. mix well. Manganese by the Periodate (Photometric) Method NOTE 29—If a special perchloric acid hood is not available. 6.0413 paper and wash thoroughly with hot H2O (See Note 30).0031 0. respectively. 0.3.0404 S-1143 0.5.7.5. Determinations 4 2 26.3.3 Ammonium Molybdovanadate Solution: 26. Dilute to volume and Dissolve 0.05.3.05 mg P/mL)— solution in the reference cell. Store in a dilute to volume and mix well.0087 solution is colorless or slightly yellow (10 to 15 min).4.1 to 500 mL with distilled standards similarly treated. Take up salts with 5 mL HCl. rous in µg/mL.3.1 The number of laboratories.5.1353 0.0.1 Manganese Standard Solution (1 mL to 50 µg Mn)— and transfer to a 100 mL volumetric flask. Evaporate cautiously to ment is made at 545 nm. Add 10 mL HNO3 and 25 mL HClO4 (See Note NOTE 31—The treatment of the residue with HF and H2SO4 may be 29). Cool the solution. Thu Jun 8 19:00:12 EDT 2017 20 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. 26. heat on a hot plate. break up residue.3.0091 0. and reproducibility.4. Cover and boil until S-1142 0. Cool.0.6 Calculation: 26. Boil up with 1 mL of HNO3 and 20 mL of water. 26. and can then be read in a photometer at a wavelength of 545 nm.2 The following precision statements are provisional. Laboratories 3 6 Materials 5 4 1. D = dilution factor.0043 0. and allow to stand for 10 C25 Minimum min. This method is capable of determining small amounts of Mn as NOTE 30—The filter paper and silica residue must be washed free of low as 10 ppm.0017 0. Cool S-1141 0.7. 27.2 Place paper and contents in a platinum crucible and nadate (See 26. transfer to a 500-mL flask and add 10 mL ammonium molydovanadate solution.2 Add 1 mL of perchloric acid and dilute to about 20 nations in this study does not meet the minimum requirements mL with water. where: mix.7.3 Special Solutions: and 1 mL HClO4 and warm to dissolve.0657 0.0122 slightly and add 50 mL H2O.30.3 Determine the absorbance of each standard solution 26.4. water.2 Dissolve 50 g of ammonium molybdate in 400 mL C 3 D 3 2. Ignite at a of manganese by periodate.3. and 14 mL of phosphorous W = g of sample.3 Pour solution from 26.2. and determi- 26. Dilute to Test Methods Practice E691 volume with distilled water.1 Calculate % P2O5 as follows: 26.5 Procedure: following test method and materials to be: 26.20. µg/mL deter- 26.3. materials. H2SO4 (1 + 9) and dilute to 1 L with water. volumetric flask.2 Phosphorous Working Standard (0. and add with a buret 0.2913 % P 2O 5 5 (22) of distilled water.0077 0. materials. a few milli- grams at a time (about 0.4 Record the absorbance at 545 nm using the blank 28. Instead.0005 0.” The Reserve filtrate. The lime is solubilized by reaction with 27.3 Calculation—Calculate normality as follows: W = g of sample.1 Transfer approximately 20 g of primary standard standard solution in reference cell as in preparation of standard anhydrous sodium carbonate (Na2CO3) to a platinum dish or curve.1 and transfer to 28.7.0072 0. add 10 mL H2O and 2 mL HNO3 and warm to dissolve.2 Summary of Test Method—The sample is slaked and dispersed with water. Cool. add potassium periodate (KIO3) crystals.2 Standardization of HCl with Na2CO3: 27. For precision develop the permanganate color by small additions of KIO3 as and bias information on standardization with Na2CO3 or directed in 27.3. 28. 5 and 10 mL of manganese C25 Minimum standard solution to six 150 mL beakers.0108 0.2 The following precision statements are provisional. SR and R.000 N)—Prepare a a 100 mL volumetric flask. Cover and boil until 28.0147 0.1 mg of the 27. evaporate to dryness twice with nitric acid and finally boil with 10 mL HNO3 and 50 mL H2O. discharged on further heating. heat on hot plate. Cool the solution. the total heating period should last about 30 cessed which does meet the requirements of Practice E691.1.3 Transfer an aliquot containing <500 µg Mn to a 150 Standardization of sock solution should be performed on a mL beaker.5.0200 0.5.6 Calculation: dried Na2CO3 and transfer to a 500-mL flask.1096 0. and compare against a set of standards similarly treated. following test method and materials to be: dilute to volume and mix.3 g total).2 Allow to cool.0020 27.0271 0. heat to near boiling and regular basis at a minimum of once per month. Ignite at a higher temperature until titration against standard acid using phenolphthalein as the ash is white.2.0010 0. Add 10 mL HNO3 and 20 mL HClO4 (See Note 32). 28. HClO4. volumetric flask. and boil % Mn 5 W 3 104 (23) the solution carefully.0005 0.1 Precision.87! /C (24) Copyright by ASTM Int'l (all rights reserved).0 g of prepared sample into a 250-mL S-1144 0. expel SiO2 with HF and H2SO4. dilute to volume and mix.3.7 Precision and Bias: A 5 ~ B 3 18. is fully developed. transfer to a 50-mL volumetric flask. 28.2 Weigh accurately 4. and reproducibility. characterized by repeatability.4 Preparation of Calibration Curve: Test Methods Practice E691 27.5 Procedure: S-1142 0.0011 0. and dry at 250 °C for 4 h.0024 0.0028 0. Cool in a desiccator. Add 50 mL of 27.1 Hydrochloric Acid. S-1145 0.0007 0.6. . evaporate indicator.3. Sr and r.0304 beaker and dampen with about 5 to 10 mL of water.2.1 Weigh 2. 1. and 28.0012 0.1 Transfer 0.2 Nitric-Phosphoric Acid Mixture—Add 800 mL 27. until the color is discharged (See Note 29).4 g to the nearest 0.1 % solution of methyl red in alcohol. 27.3 Special Solutions: Combine solution with filtrate reserved in 27. 27. Thu Jun 8 19:00:12 EDT 2017 21 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.0028 S-1141 0. Read absorbance at 545 nm using the “0” standard (blank) in the reference cell and construct a Precision Statement % Mn Color for Test Method: calibration curve by plotting absorbance versus concentration Material Average Sr SR r R of Mn in µg/mL. solution by diluting 83 mL of HCl to 1 L with CO2-free water. to dryness (See Note 31) and fuse residue with Na2CO3. transfer to a 50 mL Tris-(Hydroxymethyl) Amino-Methane see Practice E200. and determi- HNO3 and 200 mL H3PO4 to 400 mL of H2O and dilute to 2 L. 28. Keep solution near boiling for 10 min after Within five years. Filter through retentive filter enter into the reaction under the conditions of this specified test paper and wash thoroughly with hot H2O (See Note 30). 2. Titrate with C 3D the HCl solution to the first appearance of a red color. Available Lime Index evaporate to heavy fumes of HClO4.4. Add 25 Laboratories 4 6 Materials 5 4 mL of acid mixture to each and heat but do not boil. and add two drops of a 0. No further reproductions authorized. 27.0014 0.0010 0. Cool. otherwise known as the “rapid sugar test method.1 The number of laboratories.5. min.5.3.0066 27. Standard (1.2 Transfer paper and contents to a platinum crucible sugar to form calcium sucrate which is then determined by and heat until paper chars.1 Calculate the percent Mn as follows: CO2-free water. Dilute to volume and mix.0014 S-1143 0. method. until the permanganic color 27. swirl to dissolve the carbonate. additional data will be obtained and pro- color develops. interpretation of results obtained by this test method shall be NOTE 32—If a special perchloric hood is not available. 3. nations in this study does not meet the minimum requirements for determining precision prescribed in Practice E691: 27.4. Add 25 mL of acid mixture. Cool to room temperature.3.0025 0. While Determinations 4 2 heating.7. Cool quicklime and hydrated lime designates those constituents that slightly and add 50 mL H2O.2. and 28. crucible.0011 0. cooling to the first appearance of a faint red color that is not mined from calibration curve.1 Scope—The available lime index of high-calcium solution is colorless or slightly yellow (10 to 15 min).5.0004 0.2. D = dilution factor. has been determined for the 27.7. and continue the titration. where: alternating the addition of HCl solution and the boiling and C = concentration of Mn in sample solution µg/mL deter. omit the use of restricted by this definition. C25 − 11´2 27.3.4. respectively.0034 0. Add 6 drops of 3 s.000 N). Add several drops of phenolphthalein indicator W = weight of sample.4 Calculation—Calculate normality as follows: lime content varies to extremes.) Swirl at 5-min desiccator to room temperature.5 Sucrose Solution—(40 g of pure cane sugar in solid Available lime ~ CaO! . which persists for mg and dissolve in 50 mL of CO2-free water. Weigh rapidly 2.1 Calculate for CaO as follows: dry phenolphthalein in 100 mL of 95 % alcohol. g. stopper the flask loosely. Stock solution of sugar may be made or 1 mL of standard HCl = 1 % CaO if exactly for convenience.3.1 N NaOH solution dropwise with stirring until 2. acid × 100 or 1 mL of standard HCl = 1. V = standard HCl (1.4. and facilitate the dispersion and solution. Put a clean magnetic stirrer bar into the flask and place the flask on the magnetic stirrer. 28. 28.3. however. g.3.1 The sample as received at the laboratory shall be thoroughly mixed and a representative sample with minimum where: weight of 100 g shall be taken and pulverized to pass a No.3 Add 100 mL of the neutralized sugar solution (or crucible and dry in a vacuum at 70 °C for 24 h (refer to Practice approximately 40 g of pure cane sugar). tion that cold CO2-free water is used and the boiling and B = Tris-(Hydroxymethyl) Amino-Methane used. Note the endpoint and ignore any further return of color. NOTE 33—This titration can also be performed potentiometrically with 28. .1 Transfer an appropriate amount of primary stan. Mix equal portions of Bromocresol of the acid requirement from a 100-mL buret. and let stand for 15 min to react. Add 0.804 = CaO.4 When titrating (See Note 36).2 Preparation of Mixed Indicator—Mix 100 mg of 4 % phenolphthalein indicator solution and wash down the Bromocresol Green with 2 mL 0. Cool in a not be less than 10 min nor more than 20 min.1. mixed indicator (See Note 30) and titrate to a bright yellow NOTE 36—A mechanical stirrer may be used during the titration if end-point with acid. a faint pink color persists. It A = normality of the HCl solution. a better dispersion of the fine particles occurs. and in cases where the available 28.4 Procedure: 28. Tris can also be dried at 105 °C (6 5 swirl. mL. intervals during reaction.4.1. g.3. it should not be stored for more than 2. with quicklime. 28.3.704 = Ca(OH)2. equivalent to 1 mL of standard immediately stopper the flask. 28. Finish the Green and Alizarin Red S solutions to form mixed indicator. more carefully at approximately one drop per second. 50 N = normality of acid solution. No further reproductions authorized. C25 − 11´2 where: other hand.5.) Prepare a 40 % solution (w/v) using N = normality of acid solution. C = HCl solution consumed. mL. it is good practice to run a preliminary test by slow titration to determine the proper amount of acid required to neutralize the sample. and a correction where: applied to the titration. some slaking action occurs to B = Na2CO3 used.704/W (27) 28. equivalent to 1 mL of standard acid × 100.1. 28. previous analyses of the lime under test.1 to the first disappearance of the pink color. g. Remove from the hot plate. sieve for analysis. Dissolve 100 mg of Alizarin Red S 28. and containing about 40 mL of CO2-free water (See Note 35). until dissolved.804 g of the finely pulver.3. g. Adjust to stir as rapidly as possible without NOTE 34—This titration can also be performed potentiometrically using incurring any loss by spattering.1 N NaOH and dilute with stopper and sides of the flask with CO2-free water.3. mL.3 Standardization of HCl with TRIS (THAM)—[Tris.2 Procedure for Hydrated Lime—The procedure for where: determining Ca(OH)2 is the same as for CaO with the excep- A = normality of the HCl solution.3 Weigh approximately 8 g of TRIS to the nearest 0. if the lime is added to a little water.1 Procedure for Quicklime: Available lime @ Ca~ OH! 2 # . cooling steps are omitted. mL.5 Calculation: 28. Thu Jun 8 19:00:12 EDT 2017 22 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.6 Precision and Bias: Copyright by ASTM Int'l (all rights reserved). Remove stopper. On the 28. Place the flask on a hot plate the aid of a glass electrode and a calomel electrode.4. desired. The acidity of each lot of sugar can be determined. add 4 to 5 drops of 28. especially g of sample is used. and immediately add 50 mL of boiling CO2-free water to the 28.mdit> 3. first add about 90 % in 100 mL CO2-free H2O.3.2 Remove the stopper. (Reaction time should °C) for 2 h in a regular laboratory drying oven. E200).70.3. and . Swirl the flask and boil actively 1 min for complete (Hydroxymethyl) Amino-Methane]: slaking.804 g of sample is used. two days. C = HCl solution consumed.5.3.000 N). titration.4 Phenolphthalein Indicator (4 %)—Dissolve 4 g of 28. and solution. g. leading to a more rapid dissolution of the sample. and place in a cold-water bath to cool to room temperature. is possible that in the case of quicklime. pure cane sugar and CO2-free water in a large beaker and stir V = standard HCl used (1. CO2-free water to 100 mL. flask.4. dard tris-(hydroxymethyl) amino-methane to suitable dish or 28. ized sample.1.3. A 5 B/ ~ 0.4. there is a tendency for the material to cake and form lumps difficult to completely dissolve in the sugar solution later. % 5 N 3 V 3 2. Unless the operator is familiar with a suitable pH meter to a pH of 4.804/W (26) form may be used per sample in place of a sugar solution. % 5 N 3 V 3 3. As an alternative.2 Calculate for Ca(OH)2 as follows: 28. Stopper the flask.4.121136 3 C ! (25) 28.32 % Ca(OH)2 when exactly 2.804 NOTE 35—Water should not be added to the sample because. brush carefully into a 500-mL Erlenmeyer flask W = weight of sample. 3 Cool the crucible and its contents and dissolve the using the following procedures.967 0.2 Summary of Test Method—Determine the percent of NOTE 37—Do not continue heating to a point where salts begin to freeze free water. carbonate.3. . Wash the filter paper lime thereby obtaining the repeatability (r) and reproducibility and its contents ten times with hot water. % 5 % LOI 2 % ~ CO2 1FM! (30) 30.479 1. the determination may have been 29. Digest on a hot plate for 30 min at Combined H 2 O. Shaft kiln quicklime 94.2 The user is cautioned that the repeatability and the free silica. melt by heating with 150 to 200 mL of water in a 400-mL 30. ashed.337 1. g. but do not exceed 600 6 50 °C. CO2.2 Place the paper containing the insoluble matter in a platinum crucible and char the paper without inflaming at low 30. 29.398 1. the H2SO4 (1 + 1) and approximately 10 mL of HF. and accordance with the preceding sections. using a retentive paper. However. where: 29. 0. CO2. cool in a CaO increase the value of the repeatability (within lab) slightly dessicator. calcium of subsequent solution.3 Due to the lack of a recognized industry standard.3 Procedure: A = crucible + insoluble residue. Calculate combined H2O.3 Procedure: beaker.3.3. and beaker.3.2 Calculate the percentage of combined water in hy- NOTE 38—Free silica is not transformed to silicic acid by the fusion and is not affected by the caustic treatment. Increase the heat to burn off the carbon.1 Twenty-four laboratories cooperated in the testing of 29.3 Calculate the percent unhydrated oxides on the TABLE 5 Precision Data (Results in % Available CaO) as-received basis as follows (See Notes 40-42): Material Average r R Hydrated lime 71. drated lime from the LOI. Unhydrated Oxides Calculated on As-Received Basis heat. ignite and weigh (See Note 34).495 0.2 Summary of Test Method—After dissolution of a large The residue then is treated with HF and sulfuric and SiO2 expelled. Transfer the paper and residue to a tared platinum test method. and free moisture (FM) determinations as follows: Combined H 2 O. add approximately 10 g of fused and 30.6. To the warm solution.3.393 0.438 0. method have not been determined. Free Silica improperly accomplished. 30. finish the fusion at a drated lime can also be calculated. This method examined by X-ray diffraction to determine whether refractory is applicable to the determination of free silica when it exceeds or highly insoluble minerals are present. Unhydrated oxides of MgO in hy- When the fusion becomes quietly molten.05 %. C25 − 11´2 28. Discard the filtrate. 30. and weigh as free silica. evaporate to bias of this test method has not been determined.4 Filter quickly. thoroughly three high calcium quicklimes and one high calcium hydrated scrub and wash the beaker with hot water. and CaSO4 in samples of gas burner. Replicate determinations should 29. No further reproductions authorized. % 5 % LOI 2 % ~ CO2 1FM! (29) 80 to 90 °C. LOI.784 unhydrated oxides on the as-received basis are illustrated in Table 6.092 oxides is intended primarily for use with Type S hydrated lime. CaCO3. CaO.3. dull red heat not over 800 °C. first by gradual heating to prevent loss of SO3. NOTE 42—It is recognized that the results from this method of Copyright by ASTM Int'l (all rights reserved). and MgO in accordance with on top of the melt and on the sides of the crucible because of the difficulty the preceding sections. the insoluble matter including SiO2 is separated.0 g of the prepared sample in a 400-mL B = crucible minus SiO2. dilute HCl (1 + 1) to dissolve iron and other contaminants of 28. lime and hydrated lime.405 NOTE 41—This method for calculating the percentage of hydrated Rotary kiln quicklime 94. calcium sulfate. Thu Jun 8 19:00:12 EDT 2017 23 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. and the oxides fused with pyrosulfate.5 Precision and Bias—The precision and bias of this test wash several times with hot water. as follows: silicic acid (See Note 37).3.001 g. cautiously add approximately 12 30.6. and the reproducibility value (between labs) noticeably.1 Scope—Free silica is usually present in the acid. 29. and finally five times with hot water or until free reproducibility are considered adequate for the purposes of the of acid. NOTE 39—Occasionally the free silica is contaminated by compounds not decomposed during fusion or dissolved in the subsequent treatments. g. five times with hot (R) (Practice E691) data contained in Table 5. and heat to a boil. add 25 mL of HCl (1 + 1). Using a W = sample. higher levels of MgO and nonreactive crucible. Cool.5 To the ignited and weighed residue add 2 drops of 28. 29.4 Calculation—Calculate the percent free silica as fol- The silicic acid liberated from the clay minerals in the lows: insoluble matter is dissolved in a hot solution of sodium Free silica. retentive paper. then be made to verify the validity of the results. Fuse thoroughly over a calculate combined water. g. and unhydrated magnesium oxide 29.1 Weigh 5. ignite at 1000 °C to constant weight.6.963 NOTE 40—The calculations involved in determining the percentage of Magnesian quicklime 88. it is possible to blend thoroughly with a small spatula.3.1 Scope—From the analytical determinations made in powdered KHSO4 or K2S2O7 in the platinum crucible. or the residue insoluble residue of lime and limestone samples. filter the insoluble matter including SiO2 and 29. dryness. 29. If the mass of the residue exceeds 0.1 Calculate percentage of combined water in quicklime g of NaOH pellets a few at a time to dissolve the precipitated from the loss on ignition and CO2 determinations. % 5 ~ A 2 B ! /W 3 100 (28) hydroxide but the free silica is unaffected. 29. sample of lime or limestone. SO3.367 0. 3.3.5 Calmagite (magnesium + calcium indicator)—1- MgO as determined from preceding sections to obtain the (hydroxyl-4-methyl-2 phenylazo)-2 naphthol-4 sulfonic acid percentage of unhydrated MgO on the as-received basis. the HCl (1 + 9) and dilute to 1 L with distilled water. Standard Solution (1 N)— Combined water 2 H 2 O ~ D ! Dissolve 56 g of KOH in 1 L of distilled water. designed to follow routine separations. Both CaO and MgO are then titrated from a 30. assays can be run directly without prior separation of the 31.34 CaO 42.3 Ammonia Buffer (pH 10. on a suitable carrier. Experience indicates. 31. 31.68 – 25.5 g of (35) NH4Cl in 300 mL of distilled water.2. NOTE 43—Both the hydroxy naphthol blue and Calmagite indicators are Total MgO 2 MgO equivalent ~ F ! 5 unhydrated MgO (37) manufactured by Mallinckrodt Chemical Works.1 Scope—This test method is a rapid EDTA complexo. however. No further reproductions authorized.70 calculation may not be in strict accord with the actual composition of the 31.3. 5 equivalent H 2 O ~ E ! as Mg~ OH! 2 31.3. single dehydra. 30.48 × 0. MgO is calculated by subtracting the EDTA equivalent to CaO present from the EDTA equivalent to Hydrated CaO ~ C ! 3 0.5 with KOH solution and titrated Total CaO 2 ~ A1B ! 5 hydrated CaO~ C ! (33) with EDTA to a blue end point using hydroxy naphthol blue as the indicator.3.238 = equivalent MgO = 25. add 570 mL of NH4OH. The assays may also be made after a direct HCl decomposition 30. C25 − 11´2 TABLE 6 Example of Calculation.3.09 – 13.3. % Values Factors Calculated Values.3.6 Hydrochloric Acid (1 + 1).3 Reagents: (34) 31.603 g of magnesium metal turnings in HCl ing action of EDTA at appropriate pH levels.3.3.2 Subtract the sum of these CaO equivalents from the 31. The value obtained by this calculation shall be reported to the nearest 0.94 × 0.4 Hydroxy Naphthol Blue (calcium indicator)— Disodium salt of 1-(2-naphthol azo-3.11 Magnesium Standard Solution (1.275 5 equivalent CaO~ A ! as CaCO3 (31) quantities to cause problems. 31. For expediency.6 disulfonic acid)2 H 2 O ~ E ! 3 2.7 Hydrochloric Acid (1 + 9).3.3.3.3213 = equivalent H2O = 13.3. Each indicator is a diluted mixture of dye plus an inert carrier. and dilute to 1 L with distilled water. 31. Unhydrated Oxides Values Determined From Residual Compound Chemical Analysis.700 = equivalent CaO = 0.1 In this test method.785 g of CaCO3.98 = unhydrated MgO = 4. primary standard grade. Ordinarily the EDTA procedure is of KCN in 100 mL of water.00 mg MgO/ combined oxides of iron and aluminum by using the complex.3.3 For the determination of calcium.6 Subtract this MgO equivalent (F) from the total 31.51 SO3 0.00 mg CaO/mL)— tion of silica and a single precipitation with NH4OH of the Weigh 1.79 – (0. Dissolve in combined oxides of iron and aluminum.40 × 1. 31. 30.275 = equivalent CaO = 0.3.5 %. Louis.10 Calcium Standard Solution (1.2.2 Potassium Hydroxide.4 Subtract this value for H2O (D) from the combined dihydrogen ethylenediamine tetraacetic acid in water and dilute water as calculated in 30. calcium and magnesium are material. Thu Jun 8 19:00:12 EDT 2017 24 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.238 5 equivalent MgO ~ F ! as Mg~ OH! 2 (36) naphthol-4-sulfonic acid on suitable carrier. the interferences may be sup- SO3 3 0.3213 CaO + MgO.3 Calculate the H2O equivalent of the remaining CaO solution buffered to pH 10 with NH3 · NH4Cl using Calmagite as follows: as the indicator. NH4OH group during a routine analysis of lime and limestone.2 If interfering elements are present in large enough CO2 3 1.34 = 0. Calcium and Magnesium Oxide (Alternative EDTA 31.9 Potassium Cyanide Solution (20 g/L)—Dissolve 2 g and limestone products. that is.3.3.61 × 2.2.8 Triethanolamine (1 + 2).700 5 equivalent CaO~ B ! as CaSO4 (32) pressed by the addition of complexing or masking agents such as triethanolamine or cyanide.3.5 Calculate the MgO equivalent of the remaining and dilute to 1 L. St.98 MgO 30.2.3. that these results provide an determined by EDTA titration after separation of silica and the index to the performance of the material in practice. 5 equivalent H 2 O ~ D ! as Ca~ OH! 2 31.48 H2O 25.51 + 0.3. 31.3.2 Summary of Test Method: 31.4 %)—Dissolve 4 g of disodium 30. % CO2 0. mL)—Dissolve 0. MO.4 Apparatus: Copyright by ASTM Int'l (all rights reserved).1 Calculate the CaO equivalents of the CO2 and SO3 followed by removal of the silica and insoluble. as follows: 31.5)—Dissolve 67. Titration Method) 31. the solution is total CaO: adjusted to a pH of 12 to 12.1 EDTA Solution (0.85) = 41.1 and 30.3. to 1 L. metric method for determining calcium and magnesium in lime 31.3. water (E) as follows: 31.48 = 11. 30. .3. 58 0. and basic and prescribed disposal procedures used.5. NOTE 45—The use of a magnetic stirrer with light may be very helpful in detecting the color change. Dissolve residue in 25 mL of HCl (1 + 9). they should first be removed by a double 31. Subtraction of the EDTA flask and transfer to an Erlenmeyer flask.5.5. Sample CaO Repeatability 1 Reproducibility 1 Tested Found sigma sigma 31.5 Magnesium Oxide: on hot plate.6.58 0.4. Presence of a large precipitate can cause loss of sharpness in the end point.4.19 0.4 Calculation: 31. Tested Found Laboratories Laboratories A-1a 1.28 0. dry the sample at 110 °C to (See Note 45).2 to 0.4.18 CaO titer.88 0.3 to 0.1 Pipet a 20-mL aliquot of the acid solution from the to about 100 mL with water.4.6.00-mg/mL stan.29 0. Add EDTA iron and aluminum with ammonia can be used for the Ca and standard solution equivalent to calcium titration.2 If the sample is known to contain significant ~ mL EDTA solution used in CaO titration ! quantities (>1 %) of iron. NOTE 47—If silica and phosphate or excessive amounts (>5 %) of iron and aluminum are present. Add 0.1 to a clear blue end point 31.3 Add 0. dard MgO solution into an Erlenmeyer flask and add 100 mL Warning—Cyanides should be used with utmost care be- of distilled water. dilute 31.. Titrate solutions must not be poured down laboratory sinks. and digest at low heat for 15 min.27 31.45 0.6.3 g of hydroxy naphthol blue indicator 31.31 0.92 0.23 0. TABLE 7 Precision of Calcium Oxide 31. transfer to a 250-mL volumetric 31. 31.6. add about 10 mL of EDTA Pooled . g Copyright by ASTM Int'l (all rights reserved).. and carefully evaporate to dryness 31. pH 12 or higher.6. dilute to volume with distilled water.6. To L-1 53. buffer to pH 10.5 Standardization: A-1a 53. Such with disodium EDTA. 0. They should be kept ammonium chloride-ammonium hydroxide buffer solution. if the standard procedure has been 31. MgO titer. 31.4.6 Procedure: (See Note 39) and titrate as in 36.2 Weigh 0. Thu Jun 8 19:00:12 EDT 2017 25 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.4. constant weight and cool to room temperature. Adjust to pH 10 with 10 mL of the cause they can be very toxic compounds. and let settle or filter using a medium textured paper.22 0. ammonia precipitation as in the standard procedure. Adjust to pH 12 to 12.4 % EDTA flask. and heavy metals (See MgO.1 If using limestone. % 5 mL EDTA equivalent to MgO (42) Note 47). g (40) add 10 mL of HCl (1 + 1). Continue the analysis as follows: approximately 0. transfer to a 250-mL volumetric flask.4 g of Calmagite indicator (See Note 44).31 titrating solution. the filtrate remaining after the precipitation of the nolamine (Warning—See 31.25/weight of sample.22 preference.2 to 0. if mL EDTA solution equivalent to MgO 5 (41) necessary.6.4 The titration determines both the calcium and 31.1 Calcium—Pipet 10 mL of standard CaO solution into A-2b 30.6. Waste cyanide add 0. and stir.3 Alternatively.1 Magnetic Stirrer with light.1 Pipet a 20-mL aliquot from the 250-mL volumetric magnesium present in solution.21 0. % 5 CaO titer 3 mL EDTA 3 1. dilute to volume. Dilute to 150 mL titration obtained for calcium from the total titration gives the with water. or 10 mL of triethanolamine and 1 drop of trietha- aluminum.58 0. and letting the solution stand for 24 h.6. 31.2) (See Note 47). 0. C25 − 11´2 31.5 Calculation: NOTE 46—Precipitation of calcium hydroxide can be prevented. Cool.. mg/mL 5 10 mg MgO standard⁄mL EDTA titration (39) 31. TFE-fluorocarbon-covered. Titrate three or more Repeatability Reproducibility aliquots and use the average to calculate the titer of the CaO Sample MgO Within Between solution. with sodium hydroxide. or 10 mL of triethanolamine. adjust the pH to 12 with about 30 mL of 1 N KOH titration value for magnesium.3 g of hydroxy naphthol blue indicator (See Note 44) and complete titration to TABLE 8 Precision of Magnesium Oxide a clear blue end point (See Note 45). 3MgO EDTA titer 3 1. . noting the color change from a red to solutions can be rendered relatively harmless by making them deep blue end point (See Note 45). 31. manganese. and mix. but if Mallinckrodt reagents are used. then add Mg EDTA determination. solution.2 Add 2 to 3 drops of 2 % potassium cyanide used to determine the silica and insoluble and iron and solution.2 Magnesium—Pipet 10 mL of the 1. The end point is the first definite blue color that remains stable for at least 30 s. No further reproductions authorized.98 0.25/weight of sample.24 dosages are considered the proper amounts to add for easy end point Pooled .5.24 0.4 Calcium Oxide: 31.28 prevent precipitation of calcium.4. add about 20 mL of ammonia mix. Acidify the filtrate with HCl.41 NOTE 44—The amount of indicator is usually a matter of individual L-1 0.2 Stirring Bar.5 with about 15 mL of 1 N KOH solution and stir.5.31 0.5. adding aliquots and use the average to calculate the magnesium titer.6.5.30 0. CaO.41 an Erlenmeyer flask and add 100 mL of distilled water. add 2 to 3 drops of 2 % potassium cyanide solution. and stir. solution (See Note 45). ~ mL EDTA solution used in CaO1MgO titration! 2 31.26 P-1a 53. Titrate three or more strongly basic. mg/mL 5 10 mg CaO standard⁄mL EDTA titration (38) A-2b 21.6.5 g of the dry sample into a 250-mL beaker. by adding one half to one third of the estimated volume of disodium EDTA solution before the addition of the potassium hydroxide. the recommended P-1a 1.28 detection. Dilute with 100 mL of water.3 Titrate to a blue end point with the 0.6.6.4 g of Calmagite indicator (See Note 39). calcium hypochlorite.5..48 0.6.6. 250-mL volumetric flask and transfer to an Erlenmeyer flask. NOTE 48—The accuracy of this test method is dependent to a large 31.3.7.3.3.2 Test the furnace and the analyzer to ensure the sample. as follows: make the necessary adjustment of the collect relay as provided 31.2.1.31 absolute units.4. in which case the manual of instructions supplied with 8 Supporting data have been filed at ASTM International Headquarters and may each instrument should be adhered to very closely and the instructions be obtained by requesting Research Report RR:C07-1000.2.1 Assemble the apparatus. 32.2 Treat each standard as directed in 32.2 32.5.3.2 0.7. sample.2 Proceed as directed in 32.5.2.3 The overall precision (1 sigma) within laboratories approximately 0. check the CO2 collection time which should have laboratories using three limestone and one dolomite reference an 80 to 90-s time duration.02 to 1 % carbon (See Note 48). C25 − 11´2 31.6.4 The overall precision (1 sigma) within laboratories extent on the accuracy of the methods used to certify the carbon for MgO is 6 0. run a duplicate 32.428 % should read 0.2.1 Select NIST steel calibration standards containing 31.6.2. No further reproductions authorized.1 Combustion Furnace and Carbon Determinator— guidelines: This unit is commercially available. ries (reproducibility) for CaO is 6 0. proceed to 32.6.4.3 Oxygen Cylinder with Two-Stage Regulator. consisting of a sulfuric acid tower.5–1 1.4 Reagents: The carbon reading should be within 6 1 % of the standard 32.6.1 to 32. % 32. bulb containing Anhydrone. correct it.3 After the instrument has been prepared for 31. using the following 32.4 manufacturer of the instrument.2. concentration in the calibration standards as well as upon their homoge- neity. 32.3.7.1–0. for in the manual of instructions.433 to 1500 mL/min and the carrier gas flow at the rate recommended 0. Start the flow of oxygen at standard which has a standardized value of 0.6.3. oxygen past a thermal conductivity cell which senses the and repeat the steps as directed in 32.3 Repeat 32.6.6 If the second sample has approximately the same connections.2.6. 32.7. determine the cause. Thu Jun 8 19:00:12 EDT 2017 26 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. a carbon 32.009.3 Calibration Curve: and electronically converted to % C which is displayed on a 32. other slightly lower than the carbon concentration of the 32.3. 32. Tests made on NIST steel standards have shown that they are 32.6. 32.3.009. Total Carbon by the Direct Combustion-Thermal sufficiently homogeneous to permit the use of samples as small as 20 mg.6.28 absolute units. er’s manual of instructions.3.1 0.4 Run the high standard first and observe the reading. (repeatability) for CaO is 6 0. amount of CO2 present. The collection time can be checked samples. oxygen using an induction furnace. 32. 32.6. % Standard. The products of combustion are swept into the carbon obtained.1 to 32. range. 0. followed. If it is out of this range.5 0.1 This test method covers the determination of carbon in since the last sample was run and determine the blank reading lime and hydrated lime samples having a carbon concentration as follows: in the range from 0.0 0. % Carbon in Sample High-Carbon Low-Carbon Standard. carbon value plus the blank (See Note 49). The CO2 is later released and swept by a fresh stream of 0.2 Condition the analyzer if more than 2 h have elapsed 32.7.6.5 If the reading is out of this range.6. NOTE 50—Not all manufacturers may have this particular feature in their instrument. using carbon standards that bracket the percent carbon in the 32.2 Copper-Tin Accelerator.7.6.1 0. The signal from the sensor is amplified 32.1 The overall precision (1 sigma) between laborato.24 absolute units.22 absolute units.6. with a blank reading of 0.4 The normal blank reading should be 0. 32. analyzer where the CO2 is selectively absorbed by a molecular 32. 0.01 32.02–0.3. adjust the slope control (See Note 50) calibration and sample analysis according to the manufactur.3. to bring the reading to within the tolerance of the standard.1 The precision of this test method was tested by ten calibration. 32.2 Crucibles—Use crucibles recommended by the 0.7.3 Select two standards.1.7 Precision and Bias:8 32. an absorption bulb containing Ascarite and another absorption 32.2. to convert CO to CO2.005 to 5 %.7.3.2 The overall precision (1 sigma) between laborato- ries for MgO is 6 0.2.2–0.1 through 32. Copyright by ASTM Int'l (all rights reserved).6 Combustion Tube with Built-In Jet. Under some conditions.6.4 Purifying Train. If it is outside of this range.3. A flowmeter precedes the induc.1 and 32.441.2 Summary of Test Method—All the carbon in the sample is converted to CO2 by combustion in a stream of purified 32.4.2 0.1 0. Prepare the induction furnace and analyzer for value as the first sample.1 The calibration of the analyzer should be done digital readout panel. 32.3 Apparatus: samples estimated from previous tests. The results shown in Tables 7 and 8 are summarized by operating without a sample.7.2 a sufficient number of CO is formed and a catalyst furnace is used to convert it to times to establish that low and consistent blank readings are CO2.1.5. If it is within this 32.6 Calibration: 31. .1 Load into a crucible 1. one slightly higher and the tion furnace assembly. absence of leaks and make the required electrical power 32.5 Preparation of Apparatus: NOTE 49—For example.5 Catalyst Furnace.6.4. Conductivity Cell Method 32. 32.6 0. by the manufacturer of the apparatus.6.1 Iron Chip Accelerator.6. low-carbon.5 g of iron chip accelerator and 1 g of tin-coated copper.007 to sieve.7.1. Place the crucible on the furnace pedestal.10 If the reading is out of the tolerance range.5V AN)— 2 to 5 0.3. run a 33. 60 (250-µm). refer to the Bromocresol Green with 2 mL of 0. Calculate CCE as described in 33. and flush the system for 30 s. manually tor.3 Phenolphthalein Indicator Solution (1 g/100 mL)— Carbon Content.6.1 to 2 0. weigh the material. 33.2 Weigh duplicate samples to the nearest 1 mg.4. determine the cause.6. the following guidelines: 33. CO2-free water to 100 mL.6.7 Procedure: N solution of hydrochloric acid (HCl) and standardize.1 Weigh and dry the limestone and slag samples to B = sample mass.3 from the reading found in 32. For further information on prepara- 32. and 33. .6.3. Sodium Hydroxide Standard Solution.0 carbonate equivalents (% CaCO3). and Carbon.1 Stabilize the furnace and analyzer as directed in available lime index test method for procedure on standardiza- 32. but not to silicate materials)—Proceed Copyright by ASTM Int'l (all rights reserved).0 N)—Prepare a 1.6 Procedure: 33.1 pH Meter. and repeat the standardization procedure. %.0 g phenolphthalein in 100 mL of alcohol. Thu Jun 8 19:00:12 EDT 2017 27 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.1 Indicator Titration Method—Using Table 9 as a is used to determine the neutralizing capability of a calcareous guide (See Note 51).4.2 Mechanical Stirrer.9 If the reading is within tolerance range.2 Potentiometric Titration Method (applicable to agri- modifiers or agricultural liming materials. raise the polyethylene bottle provided with a siphon tube and with guard pedestal into position.3.1 Standardize against 1.500 33.0 N hydrochloric acid with starts the programmer.3.1 1. or other suitable device.4 Start the cycle timer which energizes the furnace and 33. Prepare free from carbonates and store in a accelerator.6.2.3.6. Method E70.3.9.1 Scope—The calcium carbonate equivalence (CCE) test 33. and store in airtight containers. g Dissolve 1. Calculate the percentage of carbon as follows: V1 = volume of NaOH Standard Solution.5 carbon dioxide—free water. hydrated lime and pulverized slags (from indicator. where: 33.5.6.6.5. Use lime samples as received. conforming to Sections 4 and 5 of Test sample analysis.6.250 Dissolve 20 g of sodium hydroxide (NaOH) in 150 mL of 32. readjusting the slope control to bring the high standard within 33. Record the as-received and dry weights in order to calculate moisture 32.5.3 Transfer the sample to a combustion crucible.000 0.0 32.6.7.4 and record the net where: reading. Not all neutralizing components of acal- lower than the sample as directed in 32.11 If the standards are still out of line. careous material may be beneficial. Green and Alizarin Red S solutions to form mixed indicator. 0 to 0.2 Hydrochloric Acid. Standard (1. add 100 mL of 1. If the second sample has the same out of 33. three 50 mL aliquots using phenolphthalein solution as indica- tion cycle of 1 min. Cool the solution to 25 °C and g of iron chip accelerator and 1 g of the tin-coated copper dilute to 1 L.7.3.1 to 32. When the cycle is complete. 33. the production of steel) have been used extensively as soil 33. absorption of carbon dioxide (CO2) from the air: 32. % 5 A/B (43) N2 = normality of HCl Standard Solution.3. Refer to 32. 60 (250-µm) sieve.6.5 Preparation of Sample: A = net carbon content.1 N NaOH and dilute with manufacturer’s manual for instruction.9 Precision and Bias—The precision and bias of this test content. remove and discard the crucible. A measure of their cultural liming materials containing large amounts of ferrous neutralizing capability can be determined through the use of iron or coloring matter.7.3.7 Run a carbon standard that has a carbon value this method of test.3. 32. mix thoroughly.2 to in 100 mL CO2-free H2O. value plus the blank (See Note 50). 32. tolerance value as the first sample. g.8 Calculation—Subtract the value found for the blank in V1 32. add 1. No further reproductions authorized. Mix equal portions of Bromocresol 32.1 mg. proceed to 33.3.3. 33.3.8 The reading should be within +1 % of the carbon analysis is suggested. Dissolve 100 mg of Alizarin Red S correct it. Start the flow of tubes containing soda-lime. and titrate the excess 33.7.4 Sodium Hydroxide Standard Solution (0. constant weight at a temperature of 110 6 5 °C.4.3.4 to 32.4. to prevent oxygen at 1500 mL/min.4.1 Preparation of Mixed Indicator—Mix 100 mg of 32.3.6. N HCl and boil gently for 5 min. Using the variable transformer.7.6. C25 − 11´2 32. Cool.1 to 32. Record the reading. to the nearest 0. 32. Calcium Carbonate Equivalent 33.5 N NaOH solution using phenolphthalein as crushed limestone. duplicate sample.4. material and to report this value in terms of percent calcium and place into a 500-mL Erlenmeyer flask. after having set it to provide a combus.1 to 32. repeat 32. tion of hydrochloric acid.3. using tion and standardization of solutions see Practice E200.3. pass a No.7. V 2N 2 Normality ~ NaOH! 5 (44) 32. V 2 = volume of HCl used to neutralize NaOH. No.7. Take the average of the three results as the normality of the control the plate current within the range from 350 to 450 mA.4.4 Reagents: the tolerance of the standard. % Sample Weight.3 Apparatus: 32.6. 33. Grind the sample to method have not yet been determined.3 Sieve.6. therefore.2 Significance and Use—Calcareous materials such as acid with 0. the chemical 32. and lock the system.8. 3 Calcium carbonate CaCO3 97 100. g.0 % CaCO3 ~ as received! 5 @ 1 2 ~ A 2 B/A ! # 3 % CaCO3 ~ dry! (46) °C)—Dilute 25.3. dry KCl in CO2-free deionized water and dilute to 1 L. and nolphthalein in 100 mL of 95 % alcohol.2 As-received basis (limestone only): phenolphthalein as the indicator.6. 34.4 Phenolphthalein Indicator—Dissolve 4 g of dry phe- A = as received sample weight from 33. grade KCl crystals at 110 °C for 1 h.3.2 M)—Dissolve 8. It is strongly recommended that a combination pH and temperature com- 33.6 Dolomitic Type N hydrate Ca(OH)2 MgO 98 175. Thu Jun 8 19:00:12 EDT 2017 28 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. Sample Type Formula % Theoretical C.4. 34.33 1.1 Scope—This method covers the electrometric pH 34.1 g of reagent grade potassium hydrogen phthalate of material is mixed with CO2-free deionized water so that the which has been dried in an oven at 110 °C for 1 h.4. pH 7 and pH 10. Stir at a moderate speed to avoid splash. 34.5.69 2.4.4. as described in 33.2 Sodium Hydroxide Solution (0.4.1 Dry Basis: pensation probe be used. No further reproductions authorized. 50-mL Class A buret by means of a pipette.0 N HCl required for neutralization. W = sample weight.5 Commercially available pH buffer solutions. then quantitatively transfer the that an accurate measurement of pH is obtained for samples weighed material into a 400-mL beaker. Wu = sample weight used in preliminary titration.48 2.3 Hydroxide-Chloride Buffer Solution (pH 13.1 Potassium Chloride Solution (0. 34. Transfer to a 400-mL beaker with a pH greater than 11.4 Dolomitic limestone CaCO3 MgCO3 97 108. 34.1 Initial Standardization—Transfer 50. Dissolve 14. pH of Alkaline Earth Solutions 34.00 4.1.3.5.21 3. Standardize this solution with potassium acid phthalate using 33.11 3.1. Wu p 100 Wr.01 2. grams s g d 5 Vu110 where: Wr = sample weight required for testing.56 4.0N HCl used in preliminary titration. Sample Weight.0 mL of the analysis of solutions made from a variety of lime.0 6 0.4 Special Solutions: V1 = HCl solution used.5. where: 34. . . B = dry sample weight from 33. Report as CaCO3 equivalent (See Note 51).2 Summary of Test Method—In this test method a sample out 8. Accurately weigh 34.6.5 Standardization of Sodium Hydroxide Solution: 34.3 Special Apparatus: Deliver from a buret the 0. Add 185 mL of Copyright by ASTM Int'l (all rights reserved). 34.1 through “Cool. mechanical stirrer. g Magnesium oxide MgO 97 248. g. 34.1 mg) should be performed to a yellow end point using mixed indicator. mL. a preliminary titration using 2 g of sample (weighed to the nearest 0.00 g N2 = normality of NaOH solution. determine the sample weight need for testing and proceed to 33.5. mL.91 g of the V2 = NaOH solution required for titration of excess acid. Using the following formula.0045 ~ V 1 N 1 2 V 2 N 2 ! % CaCO3 ~ dry! 5 (45) should be large enough to hold all samples and buffer solutions W necessary to perform this method. 34.6 A For those materials not listed in Table 9: To determine the amount of 1. it is critical that all samples and and insert glass and calomel electrodes of a pH meter and a buffer solutions be at 25.0 mL of the NaOH solution to 100 mL with CO2-free deionized water.1 pH Meter—A commercially available pH meter ca- then dropwise until the solution attains pH 7 and remains pable of calibration with a minimum of two different buffers constant for 1 min while stirring. hydrate. mL.5 N NaOH solution rapidly to pH 5.9 Dolomitic lime CaO MgO 97 207.1.0 Calcium hydroxide Ca(OH)2 98 135.3. Record the pH of the solution is determined electrometrically.0 at 25. as in 33.3. and Vu = volume of 1. NOTE 51—It is necessary that the pH meter be equipped with a lence: combination pH electrode as well as a temperature compensation probe.1 mg.6.”.C.6 Dolomitic Type S hydrate Ca(OH)2 Mg(OH)2 98 151. .2 Constant Temperature Water Bath—The water bath 5. g.3 Calculation of Percent Calcium Carbonate Equiva.6. where: 34.E.0 mL of the KCl solution and 66. C25 − 11´2 TABLE 9 Recommended Sample WeightA Purity.2 M)—Dry reagent N1 = normality of HCl solution.6.0 °C when measured. To ensure weight to the nearest 0.3 Calcium oxide CaO 97 178. and of NaOH in CO2-free deionized water and dilute to 1 L.6. and sodium hydroxide solution to be standardized to a well rinsed limestone-bearing materials. 33. 8. the temperature of the the pH measurement.6.2019 2 0. a detailed calibration 34.2 mo. Titrate to an sured. it can be adjusted by weighed material into a 250-mL Erlenmeyer flask containing the addition of additional sodium hydroxide.7.2000 N.1979 N solution needs to immediately stopper the flask with a rubber stopper. 34. the pH measurement should be samples and buffers should be kept at 25. due to the high pH being measured. transfer 50 mL 39. and stir for 0.3 Correction if Base is “too weak”—If the molarity weight to the nearest 0. Report the pH 53).7.1 °C while they are being mea- sodium hydroxide solution to be standardized.0).0 6 0.4. Quantitatively transfer the (normality) is determined to be too weak. 34. stirrer.0 °C. . No further reproductions authorized.0 L of 0. quickly measure the pH of the brackets the pH of the sample being tested. It is imperative that the pH meter in accordance with the manufacturer’s instructions.3 Once the temperature of the sample is stabilized at NaOH 5 39.5. Quantitatively transfer the CO2-free deionized water need to be added as follows: weighed material into a 250-mL Erlenmeyer flask containing 200 mL of CO2-free deionized water.4 Correction if Base is “too strong”—If the molarity in accordance with section 34. suspension as well as to allow the sample temperature to 34. C25 − 11´2 CO2-free deionized water which is at a temperature of not cause errors to the extent that it does with samples with a pH in excess 26. 34.0021 M the desired temperature range.7. using a 50-mL transfer pipette.1 °C.2019 mole immediately stopper the flask with a rubber stopper.5.8. Follow 25. If 1.0 g of the prepared sample and record the 34.9 Precision and Bias: Copyright by ASTM Int'l (all rights reserved).0 L 3 0. A constant temperature water bath may be necessary to obtain 0.2019 N solution needs to be 34. it is imperative that solution and proceed to titrate the prepared standard with the all solutions be at 25. choose the pair of buffers which best in accordance with section 34.6.1 Weigh 10.997 g/mole 3 0. calculate how many millilitres of weight to the nearest 0.8.1 Weigh 10. magnetic stir bar. An example of this 34.1 mg. If needed.0 g of the prepared sample and record the weakened to 0.1 Using the appropriate combination of the commer. commercially available pH equipment. using a 50-mL transfer pipette. from the following equation: NOTE 53—In strongly alkaline solutions.2 Let the solution stand for at least 30 min to allow the suspended material to settle out from the suspension. of potassium hydrogen phthalate concentration of hydroxide ions is so high that the small amount of Normality of NaOH 5 (47) hydrogen ions produced by the ionization of water is sufficient to change mL of NaOH 3 factor of 0. 34.0 °C.2019 M 5 0. An example of 200 mL of CO2-free deionized water. Report the pH to four significant figures. endpoint of light pink which will persist for at least 6 s. Let the solution stand for at least 30 completed. and the Hydroxide.0 6 3. If 1.1979 mole (48) to allow the sample temperature to stabilize at 25. Standardize your sample solution (See Note 53). Using a previously standardized pH meter. and stir for be strengthened to 0. quickly measure the pH of the (normality) is determined to be too strong. sodium hydroxide need to be added as follows: 34.7 Procedure—Materials with pH Less than 11. either dilution with CO2-free deionized water or the 0. it can be adjusted by sample.5 and greater: calculation follows.0 6 0.0 6 0. as well as 1.5.6 Calibration of pH Meter—Due to the wide variety of stabilize at 25.1 °C during For samples with pH less than 11.0 L 3 0. 34.1979 M 5 0.0 °C. standardized 34. This can easily be accomplished by normality of the sodium hydroxide solution can be calculated the use of a constant temperature water bath (See Note 54).0 buffers.5. calculate how many grams of 30 min.5.5: larity specified. If all buffers and test solutions are not within this range.2 Place the sample solution into a constant temperature free deionized water needed After the addition of additional CO2-free deionized water is water bath set at 25.204228 This preliminary standardization may reveal the necessity for the pH appreciably with temperature. stirrer. to four significant figures. Add five drops of the phenolphthalein indicator For samples with a pH greater than 11. therefore the temperature is not as critical.0 L of 0.0 °C.3 Once the temperature of the sample is stabilized at procedure cannot be incorporated into this test method.1 mg.8 Procedure—Materials with pH of 11. Add a magnetic stir bar. 34.1979 M 5 0. standardized Chloride buffer (pH 13. recheck the standardization as specified in section min to allow the suspended material to settle out from the 34. temperature of the test solution remain at 25.997 g/mole 25.8.0019 L or 1. completed.5. NOTE 52—For alkaline solutions in this pH range the temperature does 34.7. this calculation follows. especially above pH 12.2000 N. of the settled solution to a 100-mL beaker containing a lar equipment.9 mL of CO2 2 (49) 30 min. large errors in the 34.6.200 5 0.0 6 2.0 6 3. 1. Add a magnetic stir bar. dissolve.4 Slowly stir the sample solution using a magnetic cially available pH 7 and pH 10. the Wt.0 °C (See Note carried out in a constant temperature water bath.0 6 0. Using a previously standardized pH meter.0830 g needed of the settle solution to a 100-mL beaker containing a magnetic After the addition of additional sodium hydroxide is stir bar.1 °C.2 M 2 0. recheck the standardization as specified in section 34. Stir this mixture gently until all of the crystals of 11.0021 mole 5 0.0 6 3.5. Thu Jun 8 19:00:12 EDT 2017 29 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.4 Slowly stir the sample solution using a magnetic 34. transfer 50 mL the manufacturer’s instructions for calibration of your particu.2 Calculation of Sodium Hydroxide Normality—The measured pH will occur. the addition of CO2-free deionized water. 2785 0.0193 0.4111 0.1 A sample of lime.6) using a check passes through the carbon and sulfur infrared detection cells standard. Sample E −325 stone 11. SR be controlled by the voltage to the coil and the accelerators and R. must be analyzed on a resistance-furnace-type unit.01 to 13 % carbon and from 0.2 Detector—The detector shall consist of one or more 35.0143 0. and for the blank due to accelerators and determinating precision prescribed in Practice E691: crucibles. Total Carbon and Sulfur by the Combustion/Infrared direct lance flow of oxygen onto the sample to combust the Detection Method remaining sample material.0684 0.9.2408 0. Serious injury or death can priate safety and health practices and determine the applicabil.2 Hydrated lime.1.5477 0.2 Resistance—The resistance furnace is an open- Sample G bottom ash 12.1 Induction—The induction furnace works by sup- Determinations: 3 2 plying power to an inductor coil.0123 0. the gas stream validated on a regular basis (See 35.1 This test method is for the determination of carbon or infrared solid-state absorption detectors for carbon or sulfur. This should responsibility of the user of this standard to establish appro.0069 0. This test method long as interference does not occur during analysis. has been determined for the following materials to be: used in combusting the sample. See manufacturer’s instructions and cautions before ity of regulatory limitations prior to use.1. to 3 % sulfur.9393 Sample F cyclone dust 12.1559 1. or both.2 Both carbon and sulfur are calibrated against a electronics are working properly.4 Reagents—Use reagents recommended by the instru- 35.2791 0.5. Thu Jun 8 19:00:12 EDT 2017 30 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.3 Apparatus: C25 Minimum Laboratories 7 6 35. These samples gasses may collect in the IR cell within the closed system. in lime and limestone. if any. It is the tor tube in the induction furnace electrical cabinet.1210 Sample C dolo 12. In the analyzer.3 Combustion Crucibles—The crucibles must be of 35.2 Summary of Test Method: 35. and determi. A purge flow of oxygen around the Sample I fly ash 11.1. lime 12. hyd.1 The number of laboratories. weighed into a ceramic crucible.6136 Sample J hydrate 12. In a pure oxygen 35.0120 0.0069 0. and 35.4090 0. accelerators are added.4073 0.0831 1. This is used to avoid heating some types of samples too Sample B waste lime 12. 35. or kiln flue dust is ment manufacturer or their equivalent. 35. Carbon These types of materials should be analyzed in a resistance results will not be similarly effected. The standards must have Copyright by ASTM Int'l (all rights reserved).2191 0.5249 keep the atmosphere out while acting as a primary source for Sample L quicklime 12.6. ment must be calibrated daily or as indicated by check the sample is fluxed and oxidized converting carbon into standards by using a standard of known carbon and sulfur CO/CO2 and sulfur into SO2.9.3. See the manufacturer’s instructions and cautions moisture content in the post-combustion gases. covers the determination of carbon and sulfur in an acceptable NOTE 54—Halogens can be a source of problems.6541 35.7814 coil. which carries the combustion Sample D dolo lime 12.0244 0. hydroxides. or sulfur.2.3821 0. No further reproductions authorized.0177 0. The check and calibration reference material or standard with known carbon and sulfur standard cannot be the same standard.3. materials.0274 0. Because of the high furnace. concentrations.6776 0.4949 combustion. and samples with high adequate thickness and capacity to retain the molten slag and moisture cannot be suitably analyzed for sulfur using an have a sulfur blank as low and consistent as possible. which interacts with the 34.5 Calibration: the crucible is placed in the furnace. The check standard is used to determine the shift-to- where measurement occurs.1. .1875 0.2 Precision Statement for Test Method: pH—Precision. changed. sample and accelerators in a ceramic crucible. or are concentration range from 0. Some instruments are supplied Materials Average Sr SR r R with a rheostat used to control the power input to the induction Sample A kiln dust 12. The detector may be packaged with the furnace unit as been adapted for use with kiln flue dusts. result.3817 0. If they are.1.0297 0.8384 front of the combustion area provides an oxygen blanket to Sample K h.0495 0. must be checked often. Combustion hydrate takes place in an oxygen stream. induction furnace unit. 35.1 Furnace: Materials 12 4 35. and reproducibility.3942 0. Test Methods Practice E691 35.1338 ended combustion system that provides an oxygen environ- Sample H fly ash 9.2994 0. only be done by trained personnel. 35.7799 products through various dust and moisture traps to a detector.0164 0.3 This standard does not purport to address all of the Warning—It is extremely dangerous to change the oscilla- safety concerns.0766 0. The second oxygen flow is delayed to start after the majority of the sample has been combusted and provides a 35.4004 0.3. C25 − 11´2 34.5.0402 0.1 Calibration Standard—This test method and instru- environment at the high temperatures generated by the furnace. it is suggested that a halogen trap be used.2998 0. This is to compensate for characteristics of a nations in this study does meet the minimum requirements for given apparatus.0260 0.3.0728 0. associated with its use.0345 0.0557 0.4049 0. Flammable released or produced from the combustion. limestone. Significant portions of SO2 will be Warning—There is an explosion hazard associated with the trapped in the dust filter which will be moist due to the water analysis of coal and coke in an induction furnace.005 suspected to be.3.1 Scope: 35.6741 rapidly during the early stages of combustion. and when needed.2 Check Standard—The instrument calibration must be then swept toward the analyzer. through a drying tube to remove the combustion moisture and 35.0459 0.1767 0.3355 0.0336 1.2199 0. This test method has also both.3193 0.4331 0.1948 0.0699 ment in two separate areas. moisture filters before analyzing any samples. present. attempting to change the oscillator tube. The combustion gases are swept content. Sr and r. The power can characterized by repeatability.2. shift variations in the test method and to verify that the 35.0194 0.2336 0.3. 2 Summary of Test Method—The sample is dissolved in analysis of the trace amounts of iron that may be present HCl and the SiO2 is dehydrated and separated from the soluble because a larger sample is used.2 Calibration Procedure: the furnace temperature was too low. check the instrument with to a nationally recognized standard.6 Procedure: NOTE 56—An anhydrone tube that has collected moisture or particu- 35. Standard Reference Mate- mended as moisture absorption/desorption of SO2 may be rial (SRM). If the pared and analyzed on a routine basis (See 35.6. reset instrument values. quicklime. 36. bumpy surface or appearance of noncombustion indicates that 35. The tube should be recommended procedures in the manufacturer’s operating cleaned.3.3.6. This practice should not be used.1 Scope—This test method permits a more accurate X1. Subcommittee C07.6. or replaced.2. available lime index.3 Analysis time is generally 65 s.3. No further reproductions authorized. hydrated determined by watching the integration time of materials. limestone. iron.1 alternative method. a material of known concentration. free 35.6. such as the Total Gravimetric Sulfur materials. unhydrated. ing samples be analyzed before instrument calibration. oxides. Since some laboratories may still wish to perform these analyses. practice of pre-igniting samples at 1000 °C causes erratic recovery of sulfur. users are advised to develop their own laboratory precision and to check against standard reference materials. When operating maintenance on furnace and detector units in accordance with the instrument.6.6.3. historical.7 Precision and Bias—The precision and bias of this test NOTE 55—It has been found through round-robin studies that the method have not yet been determined. running.6. verified by a check standard. Thu Jun 8 19:00:12 EDT 2017 31 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. chemical analysis. lime. Therefore.2. free silica. TOTAL IRON BY THE POTASSIUM PERMANGANATE TITRATION METHOD INTRODUCTION The following test methods have been published as information only and are a collection of classical methods that had historically been widely used by the industry. It values.4 Inspect the crucible for a proper burn. Keywords 35. This can be moisture. 35. or both. they have been placed in these appendixes. accurate according to the last instrument calibration. or certified upon purchase traceable late release of sulfur.6. calcium. magnesium.2.6). The precision and bias testing has not been performed for these methods. pected time.6. and record results.3 Run laboratory samples as specified in 35. Prepare calibration samples. It is possible to have bimodal curves that indicate a Method (See Section 24). classical.2 Place the sample in the instrument and perform the 36. methods. C25 − 11´2 a known carbon or sulfur content.6. 35. 35.2 It is recommended that a check standard be pre- every 10 samples to verify instrument performance. The use of 35. then find the cause and recalibrate. tolerance can be defined as 35.3. then changing of the Anhydrone tube is recom. manganese. carbon dioxide. you can also expect the analysis time to increase due to dust and moisture from combustion of the sample. aluminum.6.6. 35. and record results. loss on ignition. reference method. free moisture. The small amount of iron left in the insoluble Copyright by ASTM Int'l (all rights reserved). instrumental analysis. finding out what is a normal time for the type of sample you are (LOI).1 Weigh samples to the nearest 0. at regular intervals. either as determined occurring. oxides. silicon dioxide. X1.3.6. analyze. sulfur APPENDIXES (Nonmandatory Information) HISTORICAL ASTM METHODS X1. salts by filtration. record results and continue. limestone. When in doubt. with the manufacturer’s instructions for a specific instrument.5 After each analysis.1 mg in accordance NIST traceable standards or comparable is recommended.6. phosphorus.1 Instrumental Setup—Clean and perform routine lates may “cake” and cause your analysis time to increase. analysis. 35.6 Analyze the check standard after a minimum of 35. If analysis time for sulfur exceeds the normal ex. It is recommended that a minimum of three condition- 35. reset instrument blank 35. manual. NOTE 57—For purposes of this procedure. This is to analysis of the check standard is not within tolerance (See Note verify that routine samples tested during a specific interval are 57). Because they are presently of limited use.3 Sample Procedure: results which meet the published certified value of the standard within the published standard deviation of the standard’s certified value. analyze. A rough. carbon. and lime. they have been deleted from the main body of reference test methods. methods. Be cautious about the variability of instruments and by a reference method.1 Prepare blanks.3.3.05 encourages comments and evaluation of these methods. Check with previous blank values is recommended that samples be saved until results can be and if necessary repeat. . strontium. Thu Jun 8 19:00:12 EDT 2017 32 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. mL.2. dilute the contents of the crucible with water. and cooled to 27 6 3 °C.4.3 Special Solutions: present) of the properly prepared sample into a beaker and add X1. . and the recovered iron is combined with the bulk of 0. Heat the X1.3.004 g of ferric oxide (Fe2O3). 25 to 30 mL/min.2) where: where: N = normality of KMnO4 solution. After the reaction ceases.2. Iron is reduced with SnCl2 and titrated with KMnO4 solution. while stirring slowly. allowing each drop to become decolor. Reduce the iron by color disappears (about 60 s). (KMnO4) in 1 L of water and boil gently in a flask for 20 to 30 and precipitate the iron by adding enough NH4OH to change min. where with HF. Add 50 mL of HCl (1 + 4).3. mL of the MnSO4 solution. stopper. heat to dissolve water. Standard Solution (0.1 Manganese Sulfate Solution (70 g/L)—Dissolve 70 25 mL of HCl (1 + 1).925 = sodium oxalate equivalent to 1 mL of 1 N KMnO4 X1. Retain the filter paper.4.6 Precision and Bias—The precision and bias of this test solution. then wash the paper and contents N): several times with hot water. Allow the several days in the dark. adding SnCl2 dropwise from a pipet. and allow to stand for the color of the indicator from red to distinct yellow. the salts.1) Fe2 O 3 . filter the insoluble matter including SiO2 using a X1. Copyright by ASTM Int'l (all rights reserved). Stir and allow to stand complete the titration at this temperature by adding KMnO4 for 3 to 5 min (See Note 22). Filter into a clean beaker and wash. dilute again to 1 L. adding a few disappears (See Note 21). Cool. 14. and evaporate to fumes of sulfur H2SO4 (5 + 95).1 Dissolve 1. Cool the beaker quickly in running water. and C = sample weighed.3. g. Determine the exact Fe2O3 equivalent of the solution from the X1.3.3. also be determined.4 Procedure: X1. and warm to dissolve salts. potassium dichromate may be used in place the evaporated HCl solution in a platinum crucible.1—Alternatively. add a few drops of methyl red indicator.2 Place the paper containing the insoluble matter from NOTE X1.01 % as follows: N 5 ~ W/V ! 3 14.05 N ized before the next one is added. but no more. A blank should approximately equivalent to 0. Cool.3 Heat the contents of the beaker to 60 °C and add all at once 10 mL of HgCl2 solution. X1. which has been previously boiled for 10 min trioxide. A = 0. millilitres less of the KMnO4 solution initially.3. added very slowly while stirring constantly. Let stand until the pink X1. discard and begin again. then X1. Add 140 mL H3PO4 and 130 mL H2SO4. X1. X1.3. Titrate with standard 0. g. Add the last 600-mL of 1-L beaker containing 300 mL of cold water and 25 0. Cool. while swirling the beaker NOTE X1.3 Heat the solution to near boiling. Filter through purified asbestos or a precipitate to settle slightly.1 Weigh 2 to 5 g (depending upon the amount of iron X1. paper without inflaming. V = KMnO4 solution used to titrate the sodium oxalate B = Fe2O3 equivalent of KMnO4.4. Transfer the acidified solution to Add 40 to 42 mL of the standard KMnO4 solution at the rate of the main solution containing the bulk of the iron.2. and ignite at 1000 °C for 15 min.07984 = g Fe2O3 equivalent to 1 mL of 1 N KMnO4 solution.4. Transfer with washing to a solution until a slight pink color persists for 30 s.2. mL. Stir until the oxalate has dissolved.2.07984.60 g of potassium permanganate solution to boiling. and wash using hot water.15 g of the standard sodium oxalate. C25 − 11´2 residue is dissolved with sulfuric acid after SiO2 is expelled Fe 2 O 3 equivalent of KMnO 4 = N × 0.2 Reserve filtrate. to a 400-mL beaker.05 N KMnO4 solution used in titration. the paper.05 medium-textured paper. Add 2 or 3 drops of SnCl2 in excess.3. at low heat. Char the of potassium permanganate as in the procedure of 13.925 (X1. filter. % 5 ~ A 3 B ! /C 3 100 (X1. through X1. Add 250 mL of diluted H2SO4 and 10 to 15 mL of HF.4 One millilitre of standard KMnO4 solution will be until a permanent pink end point is obtained.5 Calculation—Calculate the percent iron oxide (Fe2O3) following: to the nearest 0. or equivalent in accordance with X1.4. Dilute to 1 L. method have not been determined. No further reproductions authorized.2—If the pink color should persist because of the addition of constantly. sodium 50 mL of hot HCl (1 + 3).2 Potassium Permanganate. KMnO4 solution.2. W = sodium oxalate. wad of glass fiber and standardize against the National Institute Dissolve contents of the paper by placing paper and contents in of Standards and Technology’s standard sample 40C.2 Transfer 0. g. and solution. the iron in the main filtrate. add 1 mL of dried at 105 °C.5 to 1 mL dropwise. evaporate the g of crystalline manganese sulfate (MnSO4) in 500 mL of solution to dryness. until the yellow color of the ferric iron just too much KMnO4 solution. increase the heat to ash X1. oxalate (Na2C2O4). The sulfate may be X2.1.1. the solution filtered. then pass a few millilitres of hot bias statements within standards was mandated. little sodium carbonate and its nitric acid solution added to the X3. the residue fused with a acid with 400 mL of water and add 80 mL of NH4OH.1—This correction is unnecessary if it can be shown that the determine the SrO present which will allow a correction for the impurities are derived from the glass of the small flask in which the percent CaO as obtained in previous sections. % 5 ~ A/B ! 3 56.1 Ammonium Molybdate Solution: stone rock. Filter immediately before more than 3 % SiO2.1) gentle agitation.1.3. X2.4) to a is considered necessary. quicklime.3 Procedure: and weigh as strontium sulfate (SrSO4).3 Special Solutions: test method is not sensitive enough for an accurate analysis at the low levels of phosphorus frequently encountered in lime. collect the insoluble matter on the smallest possible filter and wash with more of the above mixture of alcohol and ether. Treat the thoroughly dried nitrates with as little (rarely over 2 mL) of a mixture of X2. X3.2 Let the filter air dry.3 To the solution of strontium nitrate. STRONTIUM OXIDE BY THE GRAVIMETRIC SULFATE (ETHER) METHOD X2. The user is water through the filter to dissolve the strontium nitrate.4. After standing overnight in the stoppered where: flask. consisting of available.1. that the precision and bias of this test method are material other than lime or alkaline earth. sulfate and should not be allowed to stand indefinitely in the X2. ignited. cool.3. small flask of 20-mL capacity and dissolve in HNO3.1 Transfer the weighed oxides obtained in the gravi. and wash weighed as strontium sulfate (SrSO4).4 Filter the SrSO4 on a small filter paper. X2.2 Summary of Test Method—The alkaline earth oxides add a few drops of H2SO4 and a quantity of alcohol equal to the are converted to nitrates.2 Summary of Test Method—The sample is dissolved in X3. Ignite at low temperature.3. The precipitate of strontium and strontium nitrate in absolute alcohol and ether are used to sulfate is allowed to develop and settle at room temperature for separate the two metals from each other. B = original mass of sample. nitric acid solution to precipitate phosphorus as ammonium X3. Peroxide containing ethers should not be distilled unless the peroxide is first X2. and X2.1 Solution A—Add 400 mL of nitric acid to 600 mL of water. let solution stand for 24 h.1 Calculate the mass of strontium oxide as follows: equal parts of absolute alcohol and ether as may be needed to dissolve the calcium salt.1 Scope—There may be certain applications that require therefore be deducted from the mass of the lime determined by a separate determination of strontium content or an exact the gravimetric method (See Section 16). A few cautioned to verify by the use of reference materials.2 Deduct the percent SrO from the percent CaO destroyed by a suitable agent such as sodium sulfate or ferrous determined in Section 17. Copyright by ASTM Int'l (all rights reserved).3 Add Solution B to Solution A slowly with constant other. again ignite.41 (X2. hydrate. on standing which are highly explosive. An HF-HNO3 treatment is included if the rock contains stirring. or lime phenolphthalein indicator. whose mass should adequate for the contemplated use. with 50 % alcohol.2 Solution B—Dissolve 118 g of 85 % molybdic dilute nitric acid. SrO. . tested spectroscopically for traces of calcium and barium if it metric determination of calcium oxide (See Section 5.3. then back-titrated with standard acid in the presence of ing phosphorus in samples of limestone. nitrates of calcium and strontium were evaporated. PHOSPHORUS BY THE TITRIMETRIC METHOD X3. Mix and cool.1 Scope—This is a titrimetric test method for determin. The phosphomolybdate is dissolved in an of potassium nitrate (KNO3) in water freshly boiled to expel excess of a standard solution of sodium hydroxide which is CO2 and cooled. This test method is designed to NOTE X2. After filtration. X3.3. X3. and Warning—Ethers tend to form peroxides by air oxidation 56. Cool.5 Precision and Bias—This test method was originally laboratory.4 Calculation: rate to dryness and heat at 150 to 160 °C.3. if tenths of a milligram of residue may remain. A fairly large sample weight is required because this X3. No further reproductions authorized. Dilute to 1 L. the a period of 12 h. Thu Jun 8 19:00:12 EDT 2017 33 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. moisten with dilute H2SO4 (1 + 1). C25 − 11´2 X2. strontium nitrate precipitate is dissolved with water and the strontium precipitated with H2SO4 filtered. A = mass of SrSO4. X2. g. The different solubilities of calcium volume of the nitrate solution. evaporate to dryness. Evapo.41 = molecular ratio of SrO to SrSO4 × 100.2 Potassium Nitrate Solution (10 g/L)—Dissolve 10 g phosphomolybdate. determination of calcium. Ammonium molybdate is added to the using. in a small beaker X2.3.4.3. approved for publication before the inclusion of precision and X2.3. X3. hastening solution by occasional. 2 Accurately weigh about 1 g of the dried standard Discard the paper.3.4 Filter into a 500-mL Erlenmeyer flask and wash with hot water. 84 or benzoic acid. and overnight (12 h). H2SO4 to 1 L with water that has been freshly boiled and Wash the stopper and sides of the flask with CO2-free water. saturated solution of barium hydroxide mg of ferric nitrate salt (Fe(NO3)3 · 9 H2O) (See Note X3. As the actual composition of the precipitate about 75 mL of CO2-free water. Evaporate N = normality of NaOH solution. Add 10 mL mL of dilute HNO3 (1 + 1) and heating on hot plate.4). brown fumes cease to come off and for several minutes X3.1).2) for every 100 mL of solution. X3.228 (X3. X3.003086) is obtained by completely before washing with the next portion of wash dividing the molecular weight of P2O5 (141. Thu Jun 8 19:00:12 EDT 2017 34 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.4.0 mL of X3.2—Phosphorus reacts to form ammonium phosphomolybdate precipitate five times with 15-mL portions of a 1 % solution of 2(NH4)3PO4 · 12MoO3.3) Ba(OH)2 (See Note X3.003086 = P2O5 equivalent of 1 N NaOH solution. dissolve in dilute nitric acid. Ignite the residue.3—Small amounts of phosphorus in the sample can be and Technology4 .4 Calculate the normality of NaOH as follows: thereafter. (The wash solution must be free of CO2. Shake the solution frequently for and 15 g of ammonium chloride (NH4Cl). and to the filtrate in the Erlenmeyer flask. The iron combines with the phosphate to form FePO4 that is very insoluble in NH4OH and affords the analyst the NOTE X3. X3.7 Return the paper and precipitate to the flask. and transfer it to a 500-mL Erlenmeyer flask.3.1 Lightly crush 5 to 6 g of standard acid potassium X3. and add V = millilitres of NaOH used.4 Procedure: Dissolve 12 g of sodium hydroxide (NaOH) in 1 L of water that X3. Place in a small glass-stoppered container and cool platinum wire through it. add 1 mL of HNO3 and 10 where: mL of HF and evaporate to dryness (See Note X3. Add 350 of a freshly filtered. NIST Standard Sample No. <3 %. Store in a stoppered flask protected then add 5 mL of NH4OH (1 + 1) in excess.) moles of NaOH in the equation) and by 1000 (number of X3. No further reproductions authorized.4.4 Sulfuric Acid.4.3.2) of the NaOH solution in grams per X3.4.4.3.5 Calculate the phosphorus pentoxide (P2O5) equivalent (See Note X3. The precipitate reacts with the NaOH solution thus: KNO3 and then wash the paper ten times with 10-mL portions 2(NH4)3PO4 · 12MoO3 + 46NaOH = 2(NH4)2HPO4 of the same solution. Standard Solution (0.2 Place the precipitating beaker under the funnel and phthalate to a fineness of approximately 10 mesh and dry for 2 punch a small hole in the tip of the filter cone by pushing a h at 100 °C.228 = gram equivalent weight of potassium acid phthalate. then add 1 mL of HNO3 E 5 N 3 0. Pour 25 mL of hot HNO3 (1 + 4) in a desiccator. Fuse residue with a W = grams of potassium acid phthalate.4.3. Standard (0. NaOH solution added. E = P2O5 equivalent of the NaOH solution.3.6 Filter through a retentive paper.3.15 N)—Dilute 4. N 5 W/V 3 204.1 Dissolve 10 g of the prepared sample by adding 80 has been freshly boiled to expel CO2.3 N)— X3.3. . make ammoniacal. Heat the solution to 40 °C and where: add 40 mL of ammonium molybdate ((NH4)2MoO4) (filtered). several hours and filter it. Standardize against the standard NaOH solution. as follows: concentrated very easily this way. NIST Standard Sample No. g/mL. opportunity to separate it from major matrix elements. Wash the flask and NOTE X3. add millilitres in 1 L).3 Sodium Hydroxide. Copyright by ASTM Int'l (all rights reserved).4. pinch of Na2CO3 (0. De. and titrate termine the ratio in strength of the standard H2SO4 solution to the excess sodium hydroxide with standard H2SO4 until the the standard NaOH solution by dividing the volume of NaOH pink color of indicator just disappears. from the CO2 of the air by means of a guard tube packed with filter on medium-textured paper and wash with diluted NH4OH Ascarite.4.4—The treatment of the residue with HF and HNO3 may be omitted if the SiO2 in the sample is low.3. Stopper the flask.3. it is essential that all the details of the procedure be leave approximately 2 mL in excess. Heat to boiling. NOTE X3. Discard the filtrate. Add 3 drops of phenolphthalein indicator HNO3 + 40 mL HCl (1 + 1). 0.5 Neutralize the nitric acid solution with NH4OH until millilitre as follows: iron hydroxide just begins to form.003086 (X3. The paper should be carefully washed + (NH4)2MoO4 + 23Na2MoO4 + 22H2O each time from the rim downward and then allowed to drain The equivalent weight of P2O5 (0. and cooled.1) X3. Add 100 mL of water and boil. and add enough standard is influenced by the conditions under which the precipitation is sodium hydroxide solution to decompose the precipitate and made.3. Reacidify with nitric acid slowly until precipitate just dissolves. cool. C25 − 11´2 X3. 39 furnished by the National Institute of Standards NOTE X3. Boil on hot plate until reddish- and titrate with the sodium hydroxide to the first pink color. Record the millilitres of followed closely as prescribed. Record the millilitres of solution by the volume of H2SO4 solution used in titration. shake for several minutes. add 6 drops of phenolphthalein indicator solution.5 g). cooled.8 Stopper the flask and shake to disintegrate the paper. Standardize against standard acid phthalate such as (5 + 95). X3. g/mL.1—Ba(OH)2 precipitates the carbonate as insoluble BaCO3. and allow to settle N = normality of the NaOH solution.3. X3. X3. 204. through the paper and wash free of iron with hot 5 % HNO3.96) by 46 (for 46 solution. twice with nitric acid to expel all the HF. standard acid.3 Evaporate the nitric acid of solution to dryness and X3.3 Add 50 mL of CO2-free distilled water and swirl to the dry salts add 30 mL of aqua regia mix (160 mL of gently to dissolve. If MnO2 excess of ferrous sulfate and then determining this excess by does not precipitate. X4. MANGANESE BY THE BISMUTHATE METHOD X4. Wash with 50 mL of X4. and W = mass of sample.0 to 2.5. . % 5 $ E ~ V 1 2 V 2 R ! % /W 3 100 (X3.5 Calculation: V1 = NaOH solution used. Heat for a few minutes or until the pink solution. Thu Jun 8 19:00:12 EDT 2017 35 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. filtering. cool to 10 to 15 °C.1) add 50 mL of the ferrous ammonium sulfate solution and titrate where: with standard KMnO4 solution to pink color.5. % 5 ~ V 1 R 2 V 2 ! N/W 3 1. manganese present).1 Scope—This is the standard titrimetric method that X4. dilute with 50 mL of HNO3 (3 + 97) and filter through asbestos or a fritted glass crucible. to a faint pink end point.0988 (X4. agitate.5 g of sodium bismuthate (NaBiO3). Ignite the residue in platinum. fuse with a little Na2CO3.5. bivalent manganese is oxidized to permanganic acid X4. R = ratio in strength of the NaOH solution to the H2SO4 X3. add more bismuthate. Section 13. Titrate the excess ferrous with 0. sample. contain enough active oxygen to correspond to at least 75 % X4. ratio (R) of the standard KMnO4 solution to the standard R = ratio in strength of KMnO4 solution to the ferrous ammonium sulfate solution by dividing the volume of Fe(NH4)2(SO4)2 solution.1 Sodium Bismuthate—The sodium bismuthate shall cold HNO3 (3 + 97) or until the washings run colorless.7 Precision and Bias—The precision and bias of this test Method.2 Dilute the solution to 150 mL and add 0. X4. used in the titration.2 Ferrous Ammonium Sulfate Solution (12 g/L)— color and then add 1.4.6 Precision and Bias—The precision and bias of this where: method have not been determined. X4.05 %.3 Apparatus: expel brown fumes.5 g of by the use of sodium bismuthate (NaBiO3) in nitric acid sodium bismuthate.05 N)—The same solution as prepared in the Total Iron.6 Calculation—Calculate the percentage of manganese Solution—Measure into a 250-mL Erlenmeyer flask. To the filtrate Mn. Add about 0. should not be encountered in significant amounts in this class of material. washing with nitric acid.5 Potassium Permanganate Standard Solution (0.5 to 1. W = mass of sample. KMnO4 solution by the volume of Fe(NH4)2(SO4)2 solution V2 = KMnO4 solution used.1 Calculate the percent P2O5 as follows: solution.0 mL in excess.5.5—Titanium and vanadium interfere in this determination but V2 = H2SO4 solution used.1 Dissolve 10 g of the sample in 100 mL of diluted samples when the concentration of manganese is at least HNO3 (1 + 1). method have not been determined. and agitate vigorously for 1 min. g/mL. add 0. adding a measured color has disappeared and MnO2 has precipitated. Record the buret Dissolve 12 g of Fe(NH4)2(SO4)2 · 6H2O in 1 L of cool H2SO4 reading. mL.1 Filtering Crucible—An asbestos Gooch crucible or NaBiO3 (or an amount equal to at least 26 times the weight of a fritted glass crucible of fine porosity.3.3 Standardization of Ferrous Ammonium Sulfate X4. Add 50 mL of cold HNO3 (3 + 97) and filter through a Gooch crucible X4. X4. Determine the V1 = Fe(NH4)2(SO4)2 solution used.5 g of X4. Standard X4.4 Reagents: or fritted glass crucible of fine porosity. and 1. NOTE X3. Boil to X4.4. N = normality of KMnO4 solution. mL.2 Summary of Test Method—After dissolution of the add the nitric acid solution of the melt to the main filtrate.4 Add enough ferrous ammonium sulfate solution (12 NaBiO3. C25 − 11´2 X3.4. Copyright by ASTM Int'l (all rights reserved).4.3) X3. g. P 2 O 5 . g. and wash the residue with hot water.5. No further reproductions authorized.3 Clear the solution by slowly adding ferrous ammo- nium sulfate solution (12 g/L) until the MnO2 dissolves.4. mL. filter.5 Procedure: may be used to determine manganese in lime and limestone X4. mL. 0.0988 = manganese equivalent of KMnO4 × 100. and X4.05 N KMnO4 solution (5 + 95). titration with a standard solution of permanganate. E = P2O5 equivalent of the NaOH solution.4 Nitric Acid (3 + 97). g/L) from a buret to discharge completely the permanganate X4. 50 mL of as follows: cold nitric acid (3 + 97). X4. it is possible to the paper and wash with hot water. Standard Solution (0. Metallic iron. FERROUS IRON BY TITRATION WITH POTASSIUM PERMANGANATE X5. cover from the beaker and rinse it off with water. In this case.3 Prepare an 800-mL beaker containing 500 mL of N)—Weigh 2. Heat if water into the funnel and cautiously open the cock so the water necessary to decompose the limestone (See Note X5.4. attacking silicates if these are present. With the aid of a stirring rod. but with dolomites.05 N KMnO4 solutions. paper into a large platinum crucible (80 to 100-mL capacity) if introduced by grinding media. the potassium dichromate method of obtainable if there is not much of such matter. Drop in a small coil of X5.3—If MnO2 is absent. Stop the stream of gas as soon as steam X5. This mode of acid decomposition lessens the danger of is usually not worth attempting because of the admixed organic matter.4. and N)—Prepare as in Total Iron.7—A determination of the ferrous iron in the insoluble matter cold acid. The beaker. that existing Discard the residue (See Note X5. but the iron will remain in solution. give a colored solution with acid. C25 − 11´2 X5. X5. it is only the there is no separation of an insoluble calcium salt which renders easier the soluble iron. acceptable results are sometimes NOTE X5. Nevertheless.3. removing the stopper.1) through a atmosphere and the soluble ferrous iron is titrated with medium-sized. NOTE X5.1. and pouring in cold water. Keep filling the funnel as fast as filter quickly (See Note X5. using NOTE X5. if not altogether.3 Potassium Dichromate. unless this addition is made with care. brought to boiling.1. But even then. X5. will also be determined as with a snugly fitting cover of transparent polypropylene and ferrous iron. and Dissolve 0. aid of heat. It is ordinarily quite sufficient to equalize the rocks is difficult if not impossible in the presence of carbona. . solution may be accomplished in a flask filled with CO2.3).4. Immediately titrate the iron solution in present).2.2—Such precaution to exclude air is hardly necessary. remove the crucible and solution contains the equivalent of 0.3. that is subsequent determination of iron in the insoluble residue.3 Special Solutions: X5. hardened filter. and if it does not titration may be substituted and HCl used instead of H2SO4.2 Add 18 mL of H2SO4 (1 + 1) and air-free water until the crucible is at least half full.1 Potassium Permanganate. however. then Matter: add a few millilitres in excess (See Note X5. Technology potassium dichromate (K2Cr2O7) or other pure.1 In Absence of Carbonaceous Matter: persists for 20 to 30 s.4.7).4. NOTE X5.2).728 g of dry National Institute of Standards and air-free water.4. Calcium sulfate X5. 12 g of boric acid. Warning—The contents of the flask may erupt violently NOTE X5. Add 3 to 5 drops of sodium diphenylamine sulfonate indicator and titrate X5. existing chiefly if not wholly as carbonate. Rinse the contents of the to determine ferrous iron in the insoluble residue.2 Diphenylamine Sulfonate Indicator Solution— escapes. Standard Method (See Section pass CO2 through for at least 10 min as the mixture is gradually 13). When the flask is cool.4. X5. pass in a stream of CO2 through a flame and tightly insert a stopper through which passes a small delivery tube and introduce dilute H2SO4 (1 + 1) till efferves- stopcock funnel. plastic funnel for the addition of acid and the escape of vapors and steam. pour cold cence ceases. While still boiling. complete. X5. heat is necessary.2 g of sodium diphenylamine sulfonate in 100 mL boil gently for 10 to 15 min.5) and may be drawn into the flask. ferrous iron thus found is mostly.3.3 Ferrous Iron in Presence of Insoluble Carbonaceous H2SO4 (1 + 1) a little at a time until effervescence ceases. or nearly so.1). in most X5. The and titrate the filtrate at once with 0. fit the cover tightly. and 20 mL of H2SO4 (1 + 3). ceous matter. and boil less rapidly on organic matter than permanganate. or until decomposition is of water. Thu Jun 8 19:00:12 EDT 2017 36 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement.4 Procedure: with the K2Cr2O7 standard solution to a purple color that X5. Quickly transfer the crucible cover and contents to the 800-mL dry K2Cr2O7 and dilute to 2 L in a volumetric flask.1—With a carbonate that is wholly decomposable without the necessary and to filter quickly. since in the presence of H2SO4 the oxidation of ferrous Copyright by ASTM Int'l (all rights reserved).4. add diluted X5.028 X5.6) through asbestos or sintered it empties until the solution in the flask amounts to 100 to 150 glass fiber (in an atmosphere of carbon dioxide if much iron is mL (See Note X5.1 Filter the titrated solution (See X5.2 Summary of Test Method—The limestone sample is decomposed with dilute sulfuric acid in a steam or CO2 X5. In the absence of carbonaceous matter.2 Ferrous Iron in the Insoluble Residue in Absence of Carbonaceous Matter: X5.3.05 N KMnO4 solution (See Note X5.4. then add a few more millilitres in excess. immediately add 7 mL of HF through the funnel.1 Weigh several grams of prepared sample into a NOTE X5. and precautions should be taken to avoid this having a plastic tube for the introduction of CO2 and a small contaminate.4—Potassium dichromate is preferred because it reacts much flask of about 250-mL capacity. water until air is expelled. add 25 mL of water.1 Scope—The determination of ferrous iron in carbonate iron is exceedingly slow. Standard Solution (0. Remove the about 250-mL capacity.05 platinum wire to prevent bumping.5 Calculation—Calculate the percent FeO as follows: cases.5—Heat is not needed with limestone if active agitation is used. Wash the filter and the residue a few times with water the flask with 0. as carbonate. No further reproductions authorized.1 Weigh 2 to 5 g of prepared sample into a flask of precipitates.2. Transfer the residue completely KMnO4.6—It is important to allow the acid to act no longer than is NOTE X5.2. internal and external pressures by opening the cock. determinable.002 g FeO/mL. 1 Steam Chamber Copyright by ASTM Int'l (all rights reserved). as shown in Fig.5 Record all weighings to the fourth decimal place. No further reproductions authorized.1. FIG. X6. pressure. thermostatically controlled. when weighing. method have not been determined.4 Procedure X6. the steam bath by a drip shield during the steaming period. X5. 10-mL Erlenmeyer flask on an amount of free calcium oxide (CaO) in high-calcium hydrated analytical balance. X6. subjected to steam at atmo. or steaming. mL. NOTE X6. Reweigh to get the exact sample weight. lime capable of being hydrated by steam at atmospheric NOTE X6.4 Place the flask and the sample in a vigorously boiling steam bath and steam for 30 min. X6.184 = equivalent weight of FeO × 100. V = titrant (KMnO4 or K2Cr2O7). X6. . dry. drying. atmosphere. X6.3 Apparatus a container of soda lime.2 Add to the flask. stopper. CO2-free medium.2—The flask should be kept stoppered at all times.4.2 Summary of Test Method to 5 g of the lime to be tested.2 The sample is dried. Remove.3 Place the flask in the drying oven that has been spheric pressure. cool in a desiccator. cool in a desiccator.1) W = weight of sample.6 Precision and Bias—The precision and bias of this test N = normality of KMnO4 or K2Cr2O7 solution.1 Weigh a clean. quicklime. or other suitable CO2-absorbing X6. Thu Jun 8 19:00:12 EDT 2017 37 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. X6. 9 This test method was taken from the Appendix of Specification C911.2 Analytical Balance. for 30 min. X6.3.184/W (X5.1—Once started.3. stopper. except (Ca(OH)2).4. Remove the flask to the oven. and weigh. again dried.4. Protect the flask in X6. TEST METHOD FOR FREE CALCIUM OXIDE IN HIGH-CALCIUM HYDRATED LIME9 X6.4. X6.1 Drying Oven.1 This test method covers the determination of the X6. dry for 30 min at 120 °C. and maintain at this temperature to CaO. and the gain in weight calculated previously heated to 120 °C.2.1 This test method is based on the principle of gain in weight of CaO when it is hydrated to form calcium hydroxide NOTE X6.3. and where: 7. % 5 V 3 N 3 7. and weigh. by means of a widestem funnel.2.3 Steam Bath.1. X6.4. complete the test without interruption. 3 X6.1 Scope X6. C25 − 11´2 FeO. X6. g.3—Oven atmosphere can be kept CO2 free by placing therein X6. Free water. Thu Jun 8 19:00:12 EDT 2017 38 Downloaded/printed by Universidad Nacional De Colombia (Universidad Nacional De Colombia) pursuant to License Agreement. % 5 3 100 S ASTM International takes no position respecting the validity of any patent rights asserted in connection with any item mentioned in this standard. W3 = weight of sample and flask after steaming and drying.astm. 100 Barr Harbor Drive. http://www. 222 Rosewood Drive.5 Calculation where: X6. follows: W2 = weight of sample and flask after drying. No further reproductions authorized. Individual reprints (single or multiple copies) of this standard may be obtained by contacting ASTM at the above address or at 610-832-9585 (phone). at the address shown below. PO Box C700. If you feel that your comments have not received a fair hearing you should make your views known to the ASTM Committee on Standards. or through the ASTM website (www. Danvers. This standard is subject to revision at any time by the responsible technical committee and must be reviewed every five years and if not revised.com/ Copyright by ASTM Int'l (all rights reserved). are entirely their own responsibility. Your comments are invited either for revision of this standard or for additional standards and should be addressed to ASTM International Headquarters. Free CaO. either reapproved or withdrawn. Tel: (978) 646-2600. 610-832-9555 (fax). Permission rights to photocopy the standard may also be secured from the Copyright Clearance Center.org (e-mail). Your comments will receive careful consideration at a meeting of the responsible technical committee. MA 01923.1 Calculate the percentage of water and CaO as W1 = weight of sample and flask before drying.1) and ~ W 3 2 W 2 ! 3 3.org).5. and the risk of infringement of such rights. .copyright. United States. West Conshohocken. which you may attend. Users of this standard are expressly advised that determination of the validity of any such patent rights. or service@astm. This standard is copyrighted by ASTM International. C25 − 11´2 X6. % 5 @ ~ W 1 2 W 2 ! /S # 3 100 (X6. PA 19428-2959.114 S = weight of sample.