Chemical Analysis of Limestone, Quicklime, and Hydrated Lime

This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles
for the
Development of International Standards, Guides and Recommendations issued by the World Trade Organization Technical Barriers to Trade (TBT) Committee.
Designation: C25 − 17
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.
1. Scope Insoluble Matter Other Than Silicon Dioxide 11

Loss on Ignition 19
1.1 These test methods cover the chemical analysis of Magnesium Oxide 18
high-calcium and dolomitic limestone, quicklime, and hy- Manganese:
drated lime. These test methods are classified as either standard Bismuthate Method Appendix X4
Periodate (Photometric) Method 27
(preferred) or alternative (optional). pH Determination of Alkaline Earth Solutions 34
Phosphorus:
1.2 The standard test methods are those that employ classi- Titrimetric Method Appendix X3
cal gravimetric or volumetric analytical procedures and are Molybdovanadate Method 26
typically those required for referee analyses where chemical Silicon Dioxide 10
Strontium Oxide Appendix X2
specification requirements are an essential part of contractual Sulfur Trioxide 23
agreement between buyer and seller. Total Carbon:
Direct Combustion-Thermal Conductivity Cell 32
1.3 Alternative or optional test methods are provided for Method
those who wish to use procedures shorter or more convenient Total Carbon and Sulfur:
than the standard methods for the routine determinations of Combustion ⁄Infrared Detection Method 35
Total Iron:
certain constituents. Optional test methods may sometimes be Standard Method, Potassium Dichromate 13
preferred to the standard test methods, but frequently the use of Titration
modern and expensive instrumentation is indicated which may Potassium Permanganate Titration Method Appendix X1
Ortho-Phenanthroline, Photometric Method 14
not be accessible to everyone. Therefore, the use of these test Total Sulfur:
methods must be left to the discretion of each laboratory. Sodium Carbonate Fusion 24
Combustion-Iodate Titration Method 25
1.4 The analytical procedures appear in the following order: Unhydrated Oxides 30
Section 1.5 This standard does not purport to address all of the
Aluminum Oxide 15 safety concerns, if any, associated with its use. It is the
Available Lime Index 28
Calcium and Magnesium Oxide: responsibility of the user of this standard to establish appro-
Alternative EDTA Titration Method 31 priate safety, health, and environmental practices and deter-
Calcium Carbonate Equivalent 33 mine the applicability of regulatory limitations prior to use.
Calcium Oxide:
Gravimetric Method 16 For specific precautionary statements, see 9.3, 10.2.1, 18.4.3,
Volumetric Method 17 31.6.4.2, X2.3.1, and X5.4.1.1.
Carbon Dioxide by Standard Method 22 1.6 This international standard was developed in accor-
Combined Oxides of Iron and Aluminum 12
Ferrous Iron Appendix X5 dance with internationally recognized principles on standard-
Free Calcium Oxide Appendix X6 ization established in the Decision on Principles for the
Free Moisture in Hydrated Lime 21
Free Moisture in Limestone 20
Development of International Standards, Guides and Recom-
Free Silica 29 mendations issued by the World Trade Organization Technical
Insoluble Matter Including Silicon Dioxide: Barriers to Trade (TBT) Committee.
Standard Method 8
Optional Perchloric Acid Method 9
2. Referenced Documents
2.1 ASTM Standards:2
1
These test methods are under the jurisdiction of ASTM Committee C07 on
Lime and Limestone and are the direct responsibility of Subcommittee C07.05 on
2
Chemical Tests. For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Current edition approved Dec. 1, 2017. Published January 2018. Originally contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
approved in 1919. Last previous edition approved in 2011 as C25 – 11ε2. DOI: Standards volume information, refer to the standard’s Document Summary page on
10.1520/C0025-17. the ASTM website.
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); Tue Jun 5 06:40:07 EDT 2018
1
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C25 − 17
C50 Practice for Sampling, Sample Preparation, Packaging, be capable of reproducing weighings within 0.0002 g with an
and Marking of Lime and Limestone Products accuracy of 60.0002 g. Rapid weighing devices that may be
C51 Terminology Relating to Lime and Limestone (as used provided such as a chain, damper, or heavy riders shall not
by the Industry) increase the basic inaccuracy by more than 0.0001 g at any
C911 Specification for Quicklime, Hydrated Lime, and reading and with any load within the rated capacity of the
Limestone for Selected Chemical and Industrial Uses balance.
D1193 Specification for Reagent Water 5.1.2 Weights—Weights used for analysis shall conform to
E29 Practice for Using Significant Digits in Test Data to Class S-1 requirements of the National Institute of Standards
Determine Conformance with Specifications and Technology as described in NIST Circular 547.4 They shall
E50 Practices for Apparatus, Reagents, and Safety Consid- be checked at least once a year or when questioned, and
erations for Chemical Analysis of Metals, Ores, and adjusted to within allowable tolerances for Class S-1 weights.
Related Materials All new sets of weights purchased shall have the weights of 1 g
E70 Test Method for pH of Aqueous Solutions With the and larger made of stainless steel or other corrosion-resistant
Glass Electrode alloy not requiring protective coating and shall meet the
E173 Practice for Conducting Interlaboratory Studies of density requirements for Class S.
Methods for Chemical Analysis of Metals (Withdrawn 5.1.3 Glassware and Laboratory Containers—Standard
1998)3 volumetric flasks, burets, pipets, dispensers, and so forth, shall
E177 Practice for Use of the Terms Precision and Bias in be carefully selected precision grade or better and shall be
ASTM Test Methods calibrated, if necessary, to meet the requirements of each
E200 Practice for Preparation, Standardization, and Storage operation. Standard-type interchangeable ground glass or TFE-
of Standard and Reagent Solutions for Chemical Analysis fluorocarbon joints are recommended for all volumetric glass-
E691 Practice for Conducting an Interlaboratory Study to ware. Polyethylene containers are recommended for all aque-
Determine the Precision of a Test Method ous solutions of alkalies and for standard solutions where the
E832 Specification for Laboratory Filter Papers presence of dissolved silica or alkali from the glass would be
objectionable.
3. Terminology 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:
Class Filter Pore Size (µm) Filter Speed
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
extremely dependent upon precautions taken during sample
preparation and analysis to minimize excessive exposure to 5.1.6 Crucibles—Platinum crucibles and tight fitting lids
ambient conditions. should preferably be made of pure unalloyed platinum and be
of 25 to 35-mL capacity. Where alloyed platinum is used for
NOTE 1—These test methods can be applied to other calcareous
materials if provisions are made to compensate for known interferences.
greater stiffness or to obviate sticking of fused material to
crucible or lid, the alloyed platinum should not decrease in
5. General Apparatus and Materials and Reagents weight by more than 0.2 mg when heated at 1200°C for 1 h.
5.1 General Apparatus and Materials: 5.1.7 Muffle Furnace—The electric muffle furnace should be
5.1.1 Balance—The balance shall be of an analytical type capable of continuous operation up to 1000°C and be capable
with a capacity not to exceed 200 g. It may be of conventional of intermittent operation at higher temperatures if required. It
design or it may be a constant-load, direct-reading type. It shall should have an indicating pyrometer accurate to 625°C.
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.
2
C25 − 17
5.2 Reagents: 6.2 Tared or Weighed Crucibles—The tare weight of cru-
5.2.1 Purity of Reagents—Reagent grade chemicals shall be cibles shall be determined by preheating the empty crucible to
used in all tests. Unless otherwise indicated, it is intended that constant weight at the same temperature and under the same
all reagents shall conform to the specifications of the Commit- conditions as shall be used for the final ignition of a residue and
tee on Analytical Reagents of the American Chemical Society5 cooling in a desiccator for the same period of time used for the
where such specifications are available. Other grades may be crucible containing the residue.
used provided it is first ascertained that the reagent is of 6.3 Constancy of Weight of Ignited Residue—To definitely
sufficiently high purity to permit its use without lessening the establish the constancy of weight of the ignited residue, the
accuracy of the determination. In addition to this, it is desirable residue and container shall be ignited at the specified tempera-
in many cases for the analyst to ensure the accuracy of his ture and time, cooled to room temperature in a desiccator, and
results by running blanks or checking against a comparable weighed. The residue and container shall then be reheated for
sample of known composition. at least 30 min at the same temperature, cooled in a desiccator
5.2.2 Purity of Water—Unless otherwise indicated, refer- for the same period of time, and reweighed. Additional ignition
ences to water are understood to mean distilled water or other periods may be required until two consecutive weights do not
water of equivalent purity. Water conforming to Specification differ by more than 0.2 mg, at which time it shall be considered
D1193 meets these requirements. that constant weight has been attained. For ignition loss, each
5.2.3 Concentration of Reagents: reheating period shall be 5 min.
5.2.3.1 Concentrated Acids and Ammonium Hydroxide—
When acids and ammonium hydroxide are specified by name 6.4 Calculation:
or chemical formula only, it shall be understood that concen- 6.4.1 The calculations included in the individual procedures
trated reagents approximating the following specific gravities sometimes assume that the exact weight specified has been
or concentrations are intended: used. Accurately weighed samples which are approximately
Acetic acid (HC2H3O2) 99.5 %
but not exactly equal to the weight specified may be used
Hydrochloric acid (HCl) sp gr 1.19 provided appropriate corrections are made in the calculation.
Hydrofluoric acid (HF) 48 % Unless otherwise stated, weights of all samples and residues
Nitric acid (HNO3) sp gr 1.42
Perchloric acid (HClO4) 70 % should be recorded to the nearest 0.0001 g.
Phosphoric acid (H3PO4) 85 % 6.4.2 In all mathematical operations on a set of observed
Sulfuric acid (H2SO4) sp gr 1.84 values, the equivalent of two more places of figures than in the
Ammonium hydroxide (NH4OH) sp gr 0.90
single observed values shall be retained. For example, if
5.2.3.2 Dilute Reagents—The concentration of dilute acids observed values are read or determined to the nearest 0.1 mg,
and NH4OH except when standardized, are specified as a ratio carry numbers to the nearest 0.001 mg in calculation.
stating the number of measured volumes of the concentrated
reagent to be diluted with a given number of measured volumes 6.5 Rounding Figures—Rounding figures to the nearest
of water. In conformance with international practice, new and significant place required in the report should be done after the
revised methods will use the “plus” designation instead of the calculations are completed, in order to keep the final results
ratio (:) symbol as the specified designation of dilution; for free from calculation errors. The rounding procedure should
example, H2SO4 (5 + 95) means 5 volumes of concentrated follow the principle outlined in Practice E29.
H2SO4 (sp gr 1.84) diluted with 95 volumes of water.
5.2.3.3 Standard Solutions—Concentrations of standard so- 7. Performance Requirements for Test Methods
lutions shall be expressed as normalities (N) or as equivalents 7.1 Referee Analyses—The reference test methods that ap-
in grams per millilitre of the component to be determined, for pear in Sections 8 through 32, or any other test methods
example: 0.1 N K2Cr2O7 solution (1 mL = 0.004 g Fe2O3). The qualified in accordance with 7.3, are required for referee
average of at least three determinations shall be used for all analysis in those cases where conformance to the requirements
standardizations. The standardization used to determine the of a chemical specification are questioned. In these cases a
strength of the standard solutions is described in the text under limestone, quicklime, or hydrated lime shall not be rejected for
each of the appropriate procedures. failure to conform to chemical requirements unless all sample
preparation and analysis of any one constituent is made entirely
6. General Procedures by reference test methods prescribed in the appropriate sections
6.1 Sampling—Samples of lime and limestone for chemical of this test method or by other qualified test methods. Excep-
analysis shall be taken and prepared in accordance with the tion can be made when specific test methods are prescribed in
requirements of Practice C50 applicable to the material to be the standard specification for the limestone, quicklime, or
tested. hydrated lime in question. The test methods actually used for
the analysis shall be designated.
7.1.1 When there is a question regarding acceptance, referee
5
Reagent Chemicals, American Chemical Society Specifications, American analyses shall be made in duplicate. If the two results do not
Chemical Society, Washington, DC. For suggestions on the testing of reagents not agree within the permissible variation given in Table 1, the
listed by the American Chemical Society, see Analar Standards for Laboratory
determination including sample preparation shall be repeated
Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia
and National Formulary, U.S. Pharmacopeia Convention, Inc. (USPC), Rockville, in duplicate until the results agree within the permissible
MD. variation. When the results agree within the permissible
3
C25 − 17
TABLE 1 Maximum Permissible Variations in ResultsA any constituent of limestone, quicklime, or hydrated lime
(Column 1) (Column 2) (Column 3) product for which a standard exists. Such demonstrations must
Maximum Difference of
Maximum Difference the Average of
be made annually.
Constituent
Between Duplicates Duplicates from SRM 7.1.3 Demonstrations shall be made by analysis of each
Certificate ValuesB
Al as Al2O3 0.20 ±0.30
constituent of concern in a SRM limestone, quicklime, or
Ca as CaO 0.20 ±0.30 hydrated lime (see Notes 2 and 3). Duplicate samples shall be
Mg as MgO 0.20 ±0.30 run on different days. The same test methods to be used for
C (lime and hydrated 0.20 ±0.30
lime) analysis of the limestone, quicklime, or hydrated lime being
C (limestone) 0.60 ±0.60 tested shall be used for analysis of the SRM. If the duplicate
Fe as Fe2O3 0.10 ±0.15 results do not agree within the permissible variation given in
Si as SiO2 0.15 ±0.30
Mn 0.05 ±0.10 Table 1, the determinations shall be repeated, following iden-
P 0.02 ±0.05
C
tification and correction of problems or errors, until a set of
Sr as SrO 0.05
S 0.03 ±0.05
duplicate results do agree within the permissible variation.
A
For demonstrating the performance of rapid test methods the SRM closest in NOTE 2—The term SRM refers to approved Standard Reference
overall composition to the limestone shall be used (see Table 2). In the case of Materials listed in Table 2.
quicklime or hydrated lime, the SRM closest in overall composition, after heating
at 1000°C for 1 h, to the product composition shall be used, except for C and S NOTE 3—There are no SRMs that are quicklime or hydrated lime as
determinations (see Note 3). supplied. When analyzing a quicklime or hydrated lime the SRM in
B
Interelement corrections may be used for any standardization provided improved carbonate form needs to be converted to closely resemble the matrix of the
accuracy can be demonstrated. product being tested. To accomplish this conversion, heat the chosen SRM
C
No SRM currently available. for 1 h at 1000°C, immediately prior to analysis and protect it from
hydration or carbonation with sealed containers and desiccation during
cooling. Carbon and sulfur may be driven off during heating, rendering the
converted SRM unsuitable as a standard for carbon and sulfur determi-
variation, their average shall be accepted as the correct value. nations. For carbon and sulfur determinations use the appropriate SRM in
For the purpose of comparing results, the percentages shall be its normal matrix.
calculated to one more significant figure than reported as
indicated in the test methods. When a blank determination is 7.1.4 The average of the results of acceptable duplicate
specified, one shall be made with each individual analysis or determinations for each constituent may differ from the SRM
with each group of two or more samples analyzed on the same certificate value by no more than the value shown in Column
day for a given constituent. 3 of Table 1. When no SRM certificate value is given, a
7.1.2 Test results from Referee methods intended for use as generally accepted accuracy standard for that constituent has
a basis for product acceptance or rejection, or for manufactur- not been identified. In such cases, only the differences between
er’s certification, can be used only after demonstration of duplicate values as specified in 7.1.3 shall apply and notifica-
precise and accurate analyses by meeting the requirements of tion of this exception shall be reported.
7.1.3, or except when demonstrated under 7.3.2.1. Such dem- 7.1.5 In questions concerning the acceptance or rejection of
onstrations may be made concurrently with analysis of the a limestone, quicklime, or hydrated lime product, upon request
limestone, quicklime, or hydrated lime product being tested. data shall be made available to all parties involved demonstrat-
The demonstration is required only for those constituents being ing that precise and accurate results were obtained with SRM
used as a basis for acceptance, rejection, or certification of a samples by the same analyst making the acceptance determi-
limestone, quicklime, or hydrated lime, but may be made for nation.
TABLE 2 Approved SRM List

Al as % Ca as % Mg as % Fe as % Si as % Sr as % Ti as % K as % Na as
(SRM) % Mn %P %S % L.O.I.
Al2O3 CaO MgO Fe2O3 SiO2 SrO TiO2 K2O % Na2O
A B
ECRM-752-1 0.12 55.4 0.15 0.045 0.70 0.008 NC 0.019 0.007 0.009 0.02 NC 43.4
IPT 35 0.24 53.8 0.70 0.14 1.98 0.009 0.003 0.04 NC 0.013 0.10 0.004 43.0
IPT 44 0.33 50.5 2.93 0.30 2.69 0.012 0.006 0.04 NC 0.019 0.12 0.002 42.9
IRSID DO 1-1C 0.55 52.69 0.60 1.04 1.99 0.022 0.022 NC 0.040 0.030 NC NC NC
NIST 1C 1.30 50.3 0.42 0.55 6.84 0.019 0.017 0.030 NC 0.07 0.28 0.020 39.9
NIST 88B 0.34 29.95 21.0 0.277 1.13 0.012 0.002 0.0076 NC (0.016)D 0.103 0.029 (46.98)
BCS 368 0.17 30.8 20.9 0.23 0.92 0.05 NC 0.0089 NC <0.01 NC (<0.01) 46.7
IRSID 702-1 0.40 30.05 20.51 0.629 2.22 0.098 0.024 NC 0.027 0.022 NC NC NC
GBW 07214 0.017 54.95 0.67 0.071 0.38 0.007 0.0011 NC 0.020 NC NC NC 43.57
GBW 07215 0.50 51.56 2.67 0.292 1.17 0.014 0.0013 NC 0.196 NC NC NC 43.22
GBW 07216 0.027 36.55 16.59 0.226 0.092 0.022 0.0018 NC 0.014 NC NC NC 46.23
GBW 07217 0.295 30.60 20.73 0.376 0.96 0.048 0.0012 NC 0.174 NC NC NC 46.30
GBW 03106 0.64 50.38 2.28 0.29 4.38 0.0055 0.006 NC 0.006 0.034 0.14 0.070 41.58
GBW 03108 0.88 47.49 3.63 1.97 3.84 0.15 0.017 NC 0.036 0.14 0.23 0.024 41.52
IPT 48 0.17 31.0 21.2 0.17 0.45 0.011 0.0096 0.009 NC 0.006 0.026 0.013 46.9
A
This SRM is still available, but its name has been changed from BCS 393 to ECRM 752-1.
B
NC = not certified.
C
This SRM has been found to be unavailable commercially. The use of private stock, though, is still allowed.
D
( ) = not certified, data for information only.
4
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7.2 Optional Analyses—The alternative test methods, as NOTE 5—An actual drawing of a curve is not required, if such a curve
opposed to reference methods, provide procedures that are, in is not needed for the method in use. A point-to-point, saw-tooth curve that
is artificially made to fit a set of data points does not constitute a valid
some cases, shorter or more convenient to use for routine curve-fitting procedure.
determination of some constituents (see Note 4). In some
instances longer, more complex procedures have been retained 7.3.3 Partial Results—Test methods that provide acceptable
as alternative test methods to permit comparison of results by results for some constituents, but not for others, may be used
different procedures or for use when unusual materials are only for those components for which acceptable results are
being examined, or when unusual preparation for analysis is obtained.
required. Results from alternative test methods may be used as 7.3.4 Report of Results—Chemical analyses obtained by
a basis for acceptance or rejection. qualified alternative test methods shall be indicated as having
been obtained by alternative methods and the type of test
NOTE 4—It is not intended that the use of reference test methods be method used shall be designated.
confined to referee analysis. A reference test method may be used in 7.3.5 Rejection of Material—See 7.1 and 7.2.
preference to an alternative test method when so desired. A reference test
method must be used where an alternative test method is not provided. 7.3.6 Requalification of a Test Method:
7.3.6.1 Requalification of a test method, as defined in 7.3.2,
7.2.1 Duplicate analyses and blank determinations are left shall be required annually.
to the discretion of the analyst when using the alternative test 7.3.6.2 Requalification also shall be required upon receipt of
methods. The final results should include the number of substantial evidence that the test method may not be providing
determinations performed and whether or not they were data in accordance with Table 1. Such requalification may be
corrected for blank values. limited to those constituents indicated to be in error and shall
7.3 Performance Requirements for Alternative Test Meth- be carried out prior to further use of the method for analysis of
ods: those constituents.
7.3.1 Definition and Scope—When analytical data obtained 7.3.6.3 Substantial evidence that a test method may not be
in accordance with this section is required, any test method providing data in accordance with Table 1 shall be considered
may be used that meets the requirements of 7.3.2. A test to have been received when a laboratory is informed that
method is considered to consist of the specific procedures, analysis of the same material by Reference Test Methods run in
reagents, supplies, equipment, instrument, and so forth, se- accordance with 7.1.1, a certified value of an approved SRM,
lected and used in a consistent manner by a specific laboratory. or an accepted value of a known secondary standard differs
7.3.1.1 If more than one instrument is used for the same from the value obtained by the test method in question by more
analysis, use of each instrument shall constitute a separate test than twice the value of Column 2 of Table 1 for one or more
method and each must be qualified separately. constituents. When indirect test methods are involved, as when
7.3.2 Qualification of a Test Method—Prior to use each test a value is obtained by difference, corrections shall be made for
method (see 7.3.1) must be qualified for each material that will minor constituents in order to put the analyses on a comparable
be tested. Qualification data or, if applicable, requalification basis prior to determining the differences (see Note 6). For any
data shall be made available. constituents affected, a test method also shall be requalified
7.3.2.1 Using the test method chosen, make single determi- after any substantial repair or replacement of one or more
nations for each constituent under consideration on the SRM critical components of an instrument essential to the test
which in overall composition most closely resembles the method.
limestone, quicklime, or hydrated lime to be tested (see Note NOTE 6—Instrumental analyses can usually detect only the element
2). Complete two rounds of tests on nonconsecutive days sought. Therefore, to avoid controversy, the actual procedure used for the
repeating all steps of sample preparations. Calculate the elemental analysis should be noted when differences with reference
differences between values and the averages of values from the procedures exist. For example, Combined Oxides of Iron and Aluminum
two rounds of tests. Blank determinations are not required, if it by Wet Test should be compared to the sum of Fe2O3 and Al2O3 obtained
instrumentally.
has been determined that blank values do not affect the validity
of the data. Blank or interference-corrected data must be so 7.3.6.4 If an instrument or piece of equipment is replaced
designated. even by one of identical make and model, or is significantly
7.3.2.2 The differences between duplicates obtained for any modified, a previously qualified test method using such new or
single constituent shall not exceed the limits shown in Column modified instrument or equipment shall be considered a new
2 of Table 1. method and must be qualified in accordance with 7.3.2.
7.3.2.3 For each constituent the average of the duplicates 7.4 Precision and Bias—Different analytical test methods
obtained shall be compared to the SRM Certificate value and are subject to individual limits of precision and bias. It is the
shall not differ from the certified value by more than the value responsibility of the user to demonstrate that the test methods
in Column 3 of Table 1. The qualification testing shall be used at least meet the requirements shown in Table 1.
conducted with newly prepared specimens.
7.3.2.4 The standardization, if applicable, used for qualifi- 8. Insoluble Matter Including Silicon Dioxide (Standard
cation and analysis of each constituent shall be determined by Method)
valid curve-fitting procedures (see Note 5). Restandardization 8.1 Scope—This test method is based on a double evapora-
shall be performed as frequently as required to ensure that the tion to dryness of the hydrochloric acid solution of the
accuracy and precision in Table 1 are maintained. limestone or lime sample to convert silicon dioxide (SiO2) to
5
C25 − 17
the insoluble form. The acid-insoluble residue of a typical 8.4 Calculation—Calculate the percentage of insoluble mat-
limestone consists of free silica and a mixture of minerals such ter including silicon dioxide to the nearest 0.01 % as follows:
as clay, mica, feldspar, tourmaline, barytes, garnet, zircon, Insoluble matter including SiO2 5 ~ A/B ! 3 100 (1)
rutile, and so forth.
where:
8.2 Summary of Test Method—After dissolution in hydro-
A = mass of ignited residue, g, and
chloric acid, the silica is dehydrated by a double evaporation to B = original mass of sample, g.
dryness. After each dehydration, the dry salts are redissolved
with dilute hydrochloric acid, the solution is filtered, and the 8.5 Precision and Bias—This test method was originally
siliceous residue and other insoluble matter separated. The two approved for publication before the inclusion of precision and
papers containing the residues are combined, ignited, and bias statements within standards was mandated. The user is
weighed. cautioned to verify by the use of reference materials, if
available, that the precision and bias of this test method are
8.3 Procedure: adequate for the contemplated use.
8.3.1 Weigh 0.5 g of quicklime or hydrated lime, or 1.0 g of
limestone ground to pass a No. 50 (250-µm) sieve (see Note 7). 9. Insoluble Matter Including Silicon Dioxide (Optional
If the sample is a limestone or hydrated lime, ignite in a Perchloric Acid Method)
covered platinum crucible in an electric muffle (see Note 8) at
950°C for 15 min or longer to effect complete decomposition. 9.1 Scope—In this test method the insoluble matter includ-
Transfer to an evaporating dish, preferably of platinum (see ing silicon dioxide is determined gravimetrically as in the
Note 9), containing about 10 mL of water, mix to a thin slurry, standard method except that perchloric acid is used to dehy-
add 5 to 10 mL of HCl, and digest with the aid of gentle heat drate the silica. The procedure is more rapid than in the
and agitation until solution is complete (see Note 10). standard method because only a single dehydration is neces-
sary. Fuming perchloric acid is a very powerful dehydrating
NOTE 7—Due to the rapidity with which quicklime and hydrated lime agent, and silicic acid can usually be completely converted to
absorb water and carbon dioxide from the air, samples must be protected the insoluble silicon dioxide in less than 20 min. This test
in tightly stoppered containers at all times. Samples for analysis are to be
weighed quickly and the sample container re-stoppered immediately after method has been determined by other agencies such as the
the sample has been removed. Association of Official Agricultural Chemists (AOAC) to be
NOTE 8—Ignition of the sample in an electric muffle is far superior to comparable to the standard hydrochloric acid method.
flame ignition. However, if an electric muffle is not available, flame
ignition and the blast lamp may be used.
9.2 Summary of Test Method—The sample is decomposed
NOTE 9—If a platinum dish is not available, porcelain may be used. A without prior ignition by a mixture of nitric (HNO3) and
glass container positively must not be used. perchloric (HClO4) acids and evaporated to fumes of HClO4.
NOTE 10—Alternatively, the loss on ignition (LOI) can be determined The fuming perchloric acid is refluxed at this temperature for
first, using 0.5 g of sample. The insoluble matter including silicon dioxide a short period of time to completely dehydrate the silica. 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. of acids and salts. The filter paper containing the residue is
8.3.2 Evaporate the solution to dryness on a steam bath. burned off, the resultant ash is ignited at high temperature until
When dry or nearly so, cover the dish and place it in an air bath the ash is white, and then is weighed.
or drying oven or on a metal triangle resting on a hot plate. 9.3 Procedure: Warning—Perchloric acid (HClO4) is an
Heat for 1 h at 100°C, remove the dish from the heat, and allow extremely reactive liquid. When using HClO4, there are pre-
the dish and contents to cool slightly. cautions to be followed which, if unheeded, may lead to serious
8.3.3 Drench the cooled mass with 20 mL (1 + 1) HCl and explosions. Contact of the hot concentrated acid with organic
place on the water bath for 10 min. Filter the mixture matter must be absolutely avoided. 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. Wash filter thoroughly with warm, diluted (HNO3) to the sample prior to fuming with HClO4. All
(5 + 95) HCl and then twice with hot water. Reserve the paper evaporations involving HClO4 must be done in a well-
and residue. ventilated hood made of nonporous and inorganic material,
8.3.4 Evaporate the filtrate to dryness, dehydrate and extract preferably Type 316L stainless steel. Facilities should be
the residue with HCl as before, but this time heat the acidified provided for washdown procedures that should be performed
solution for 1 to 2 min. Filter through a second and smaller regularly and thoroughly. These precautions on perchloric acid
piece of retentive filter paper and wash as before. Retain the use are fully discussed in Practices E50.
filtrate for iron, aluminum, calcium, and magnesium determi- 9.3.1 Weigh 0.5 g of quicklime or hydrated lime, or 1 g of
nations; combine the two wet papers containing the separated limestone ground to pass a No. 50 (250-µm) sieve. Transfer the
residues and transfer to a weighed platinum crucible. sample to a 250-mL beaker, wet carefully with a few millilitres
8.3.5 Char carefully without allowing the paper to inflame, of water, and dissolve cautiously with 10 mL of concentrated
and then ignite at 1000°C for 30 min in an electric muffle nitric acid. Add 20 mL of perchloric acid and boil until dense
furnace (see Note 8). Cool in a desiccator and weigh. The white fumes appear. If the solution darkens at this point, add
increase in weight represents the insoluble matter including several millilitres of HNO3 until the solution clears. Heat again
SiO2. to fumes.
6
C25 − 17
9.3.2 With the beaker covered, boil gently for 15 min to the amount of silica derived from the lime or limestone could
completely dehydrate the silica. Never allow contents to be important. To satisfy situations such as this, silicon dioxide
become solid or go to dryness, otherwise the separation of may be determined by volatilizing the SiO2 from the insoluble
silica will be incomplete. If this happens, add more HClO4 and residue with hydrofluoric acid and the percent SiO2 determined
repeat the dehydration. by the difference in mass obtained.
9.3.3 Cool, add 50 mL of water, heat to boiling, and filter
10.2 Procedure:
immediately using medium textured paper. Wash paper and
residue thoroughly (at least 15 times) with hot water. Test with 10.2.1 To the ignited residue in the platinum crucible (see
pH paper until washings are free of acid (see Note 11). Reserve 8.3.5 or 9.3.4), add 5 mL of water, 5 mL of hydrofluoric acid
the filtrate for iron, aluminum, calcium, and magnesium (HF), and 1 or 2 drops of H2SO4.
determinations. Warning—All acids should be handled with care, but extra
precaution is required with hydrofluoric acid. This is a very
NOTE 11—The filter paper and silica residue must be washed free of dangerous acid, harmful to eyes and skin; rubber gloves and
perchlorate salts to prevent small explosions from occurring in the
crucible when the filter paper is charred and ignited. goggles should be worn when using this acid. It does its work
silently and leaves a festering sore that is slow to heal. Any
9.3.4 Place the filter paper and contents in a weighed acid that touches the skin should be immediately washed off
platinum or porcelain crucible and heat gently with a low flame with copious quantities of water. A physician should be notified
until paper chars without inflaming, or alternatively char in an immediately if any acid is sprayed into the eyes or if prolonged
electric muffle at 300 to 400°C. Slowly raise the temperature contact with the skin occurs.
until the carbon has been burned and the ash is white. Finally,
10.2.2 Evaporate to dryness on a hot plate and heat in an
ignite at 1000°C for 30 min. Cool in a desiccator and weigh as
electric muffle at 1000°C (see Note 8) for 2 or 3 min. Cool in
insoluble matter including SiO2.
a desiccator and weigh. The difference between this mass and
9.4 Calculation—Calculate the percentage of insoluble mat- the mass of insoluble matter including silicon dioxide is the
ter including silicon dioxide to the nearest 0.01 % as follows: mass of SiO2.
Insoluble matter including SiO2 , % 5 ~ A/B ! 3 100 (2) 10.3 Calculation—Calculate the percent of silicon dioxide
where: to the nearest 0.01 % as follows:
A = mass of ignited residue, g, and SiO2 , % 5 ~ @ A 2 B ! / C# 3 100 (3)
B = original mass of sample, g.
where:
9.5 Precision and Bias: A = mass of ignited residue, g (insoluble matter including
9.5.1 Four laboratories cooperated in testing on four lime- SiO2),
stone samples and three laboratories cooperated in testing on B = mass of ignited residue less SiO2, g, and
an additional eight limestone samples thereby obtaining the C = original mass of sample, g.
precision data summarized in Table 3.
9.5.2 The user is cautioned to verify by the use of reference 10.4 Precision and Bias:
materials, if available, that the bias of this test method is 10.4.1 Three laboratories cooperated in testing on four
adequate for the contemplated use. limestone samples and two laboratories cooperated in testing
on an additional eight limestone samples thereby obtaining the
10. Silicon Dioxide precision data summarized in Table 3.
10.1 Scope—For control purposes or routine 10.4.2 The user is cautioned to verify by the use of reference
determinations, a separate analysis of SiO2 may not be neces- materials, if available, that the bias of this test method is
sary. However, for certain applications in process industries, adequate for the contemplated use.
TABLE 3 Precision Summary of Classical Test Methods

Average,A Range,A % Repeatability Reproducibility
Section Test Method % Found Found (R1, E173) (R2, E173)
8 Insol + SiO2 (Standard) ... ... ... ...
9 Insol + SiO2 (Optional) 1.405 0.09–6.40 0.184 0.351
10 SiO2 1.177 0.03–5.36 0.128 0.146
11 Insoluble Matter 0.242 0.02–0.93 0.169 0.204
12 Combined Oxides 0.459 0.22–1.21 0.181 0.282
13 Fe2O3 0.180 0.05–0.36 0.064 0.183
15 Al2O3 0.268 0.10–0.88 0.165 0.223
16 CaO (Gravimetric) 54.46 53.4–55.1 0.558 1.020
17 CaO (Volumetric) 30.57 30.4–30.7 0.371 1.132
17 CaO (Volumetric) 53.82 49.6–55.3 0.187 0.298
18 MgO (Gravimetric) 0.817 0.19–2.28 0.158 0.210
18 MgO (Gravimetric) 21.34 21.1–21.5 0.652 1.716
19 Loss on Ignition 43.73 43.6–43.9 0.158 0.463
A
Average and range of the limestones tested.
7
C25 − 17
11. Insoluble Matter oxides and the percent Fe2O3. The other metal oxides are
11.1 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- disregarded. When necessary, these metals may be analyzed
sents the mass of insoluble matter other than silicon dioxide. separately and appropriate corrections made in the Al2O3
The insoluble matter contains the remnants of any clay, analysis.
siliceous minerals, or other refractory material present in 12.2 Summary of Test Method—In this test method,
limestone. The elemental components are mainly iron and aluminum, iron, titanium, and phosphorus are precipitated
aluminum which should be removed and added to the main from the filtrate after SiO2 removal, by means of ammonium
filtrate from the SiO2 separation. If the insoluble matter hydroxide. With care, little if any manganese will be precipi-
including silica is reported as such and no hydrofluoric acid tated. The precipitate is ignited and weighed as the combined
treatment is indicated, then there is no need to make a recovery metal oxides.
of the metals and the insoluble residue may be discarded. 12.3 Special Solution:
11.2 Procedure—The insoluble matter left in the crucible 12.3.1 Methyl Red Solution (0.2 %)—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.
fusing the residue with 2 to 3 g of sodium carbonate (Na2CO3) 12.4 Procedure:
(see Note 12). Cool the melt and dissolve it in diluted HCl. Add 12.4.1 To the acid solution from the determination of SiO2
the solution to the filtrate from the dehydration and separation (see 8.3.4 or 9.3.3), add hydrochloric acid (HCl) if necessary to
of insoluble matter including silicon dioxide (see 8.3.4 or ensure a total of 10 to 15 mL of HCl.
9.3.3).
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. sium.
11.3 An alternative fusion can also be made using either 12.4.2 If a platinum evaporating dish has been used for the
lithium metaborate or lithium tetraborate as opposed to using dehydration of SiO2, or a fusion made in the platinum crucible
sodium carbonate. containing the HF-insoluble residue, iron may have been
11.4 Calculation—Calculate the percentage of insoluble partially reduced. The iron must then be oxidized by adding 1
matter other than silicon dioxide to the nearest 0.01 % as mL of saturated bromine water to the filtrate. Boil the filtrate to
follows: eliminate the excess bromine completely before adding methyl
red indicator.
Insoluble matter other than SiO2 , % 5 A 2 B (4)
12.4.3 Dilute with water to a volume of 200 to 250 mL, add
a few drops of methyl red solution, and heat just to boiling.
where: Add NH4OH (1 + 1) (see Note 14) until the color of the
A = insoluble matter including SiO2, %, and solution becomes distinctly yellow, then add 1 drop in excess
B = SiO2, %. (see Note 15). Heat the solution containing the precipitate to
11.5 Precision and Bias: boiling and boil for 50 to 60 s. Remove from heat and allow the
11.5.1 Three laboratories cooperated in testing on four precipitate to settle (not more than 5 min). Filter using
limestone samples and two laboratories cooperated in testing medium-textured paper and wash the precipitate two or three
on an additional eight limestone samples thereby obtaining the times without delay with a hot, 2 % solution of ammonium
precision data summarized in Table 3. chloride (NH4Cl) (see Note 16).
11.5.2 The user is cautioned to verify by the use of reference NOTE 14—The NH4OH used to precipitate the hydroxides must be free
materials, if available, that the bias of this test method is of any dissolved carbon dioxide (CO2).
adequate for the contemplated use. NOTE 15—At the neutral point, it usually takes 1 drop of NH4OH
(1 + 1) to change the color of the solution from red to orange and another
12. Combined Oxides (Iron, Aluminum, Phosphorus, drop to change the color from orange to yellow. If the color fades during
the precipitation or while heating, add more of the indicator. The boiling
Titanium, Manganese)
should not be prolonged as the precipitate may peptize and be difficult to
12.1 Scope—The combined oxides describe a group of retain on the filter. The solution should be distinctly yellow when it is
metals that form precipitates with ammonium hydroxide which ready to filter. If it is not, restore the yellow color with more NH4OH
(1 + 1).
may then be ignited to their respective oxides. Historically, it NOTE 16—Two drops of methyl red indicator solution should be added
has been the practice to report the combined oxides present in to the NH4Cl solution in the wash bottle followed by NH4OH (1 + 1)
limestone samples as a group because it was not always easy or added dropwise until the color just changes to yellow. If the color reverts
desirable to determine each metal oxide separately. The group to red at any time due to heating, it should be brought back to yellow by
of metal oxides consists primarily of the oxides of iron and the addition of a drop of NH4 OH (1 + 1).
aluminum, with minor amounts of titanium dioxide (TiO2), 12.4.4 Set aside the filtrate and dissolve any precipitate
phosphorus pentoxide (P2O5), and manganese oxide (Mn3O4) from the paper with 40 mL hot (1 + 3) HCl, pouring the hot
also present. Where separate determinations are preferred, the acid through the paper into the beaker in which the precipita-
combined oxides are usually weighed first, iron oxide is then tion was made. Wash the filter paper thoroughly with hot HCl
assayed separately, and aluminum oxide is finally determined (1 + 19) followed by hot water and reserve the paper. Boil the
by calculating the difference between the percent combined solution and precipitate the hydroxides with NH4OH as before.
8
C25 − 17
The precipitate is filtered through a fresh piece of medium 13.4 Procedure:
textured filter paper and washed four or five times (see Note 13.4.1 To the combined oxides of iron and aluminum (see
17) with a hot 2 % solution of NH4Cl. Combine filtrates for Ca Note 18) in the platinum crucible, add 3 to 4 g of potassium
and calcium magnesium analysis. pyrosulfate (K2S2O7). Fuse at low heat until the oxides form a
clear melt in the crucible. Cool, break up the button by gently
NOTE 17—If perchloric acid has been used, the final precipitate should
be washed at least eight times to remove all traces of perchlorate salts (see tapping the crucible on the bench, and wash fragments into a
9.3). small beaker with hot H2SO4 (5 + 95). Add 5 mL of H2SO4 (sp
gr 1.82) to the contents in the beaker, and heat to dissolve the
12.4.5 Place the moist precipitate and the two filter papers in
fused mass. Evaporate the solution to fumes of sulfuric acid
a weighed platinum crucible (see Note 9), heat slowly until the
and fume strongly for about 10 min. Cool, add 20 mL of water,
papers are charred, and finally ignite to constant weight at 1050
and warm to dissolve the salts. There may be traces of silica
to 1100°C. Cool in a desiccator and weigh.
appearing at this point, which for most routine work can be
12.5 Calculation—Calculate the percentage of ammonium ignored. If the analyst prefers to determine it, however, the
hydroxide group (combined oxides) to the nearest 0.01 % as precipitate can be filtered, washed, and ignited. The recovered
follows: SiO2 can then be added to the mass of SiO2 previously found
Combined oxides, % 5 ~ A/C ! 3 100 (5) and its mass deducted from the gross mass of iron and
aluminum reported (see Note 18).
where:
NOTE 18—When the iron is present in small quantities, it is not always
A = mass of the combined oxides, g, and desirable to determine it in the ignited oxides from the 0.5-g sample.
C = original mass of sample, g. Under these conditions, the alternative procedure should be used with a
12.6 Precision and Bias: larger sample weight.
NOTE 19—The recovered SiO2 is usually small, but could be as much
12.6.1 Four laboratories cooperated in testing on four lime- as 1 to 2 mg, even after two evaporations.
stone samples and three laboratories cooperated in testing on
13.4.2 To the sulfuric acid solution, add 10 mL HCl (1 + 1)
an additional seven limestone samples thereby obtaining the
and heat to near boiling. Add dropwise stannous chloride
precision data summarized in Table 3.
solution (see Note 20) until the yellow color of the ferric iron
12.6.2 The user is cautioned to verify by the use of test
just disappears. Add 2 or 3 drops of SnCl2 in excess.
reference materials, if available, that the bias of this test
method is adequate for the contemplated use. NOTE 20—If the stannous chloride has little effect and more than 5 to
10 mL are required, it has probably become oxidized to stannic chloride
and a fresh supply should be obtained.
13. Total Iron, Standard Method
13.4.3 Cool the mixture and add approximately 100 mL of
13.1 Scope—Iron in limestone is usually present as pyrite cold water. Add 10 mL of mercuric chloride solution, stir, and
(FeS2) with occasional occurrences of other discrete iron allow to stand for 3 to 5 min.
minerals. The amount present varies according to the location
and geological history of the deposit. During lime calcination, NOTE 21—A slight, white, silky precipitate should form. If the
precipitate appears gray or black, it indicates too much SnCl2 was added
most if not all of the iron minerals present in the limestone ore and the analysis must be repeated.
will be converted to iron oxide or sulfate.
13.4.4 Add 5 mL of H3PO4 and 3 drops of sodium diphe-
13.2 Summary of Test Method—In this test method, the total nylamine sulfonate indicator.
Fe2O3 content of the sample is determined from the ignited 13.4.5 Titrate with standard 0.05 N K2Cr2O7 solution add-
combined oxides by fusing the oxides with potassium pyrosul- ing the solution slowly while stirring constantly. The end point
fate and leaching the melt with sulfuric acid. The iron is is indicated by a change in color from green to deep blue-
reduced to the ferrous state with stannous chloride and titrated violet.
with a standard solution of potassium dichromate (K2Cr2O7).
13.5 Calculation:
13.3 Special Solutions:
13.3.1 Stannous Chloride Solution (50 g/L)—Dissolve 5 g Fe2 O 3 , % 5 ~ A/C ! 3 B 3 100 (6)
of SnCl2 · 2H2O in 10 mL of HCl and dilute to 100 mL with
water. Add several pieces of mossy tin metal to the bottle to where:
preserve the SnCl2 solution. A = K2Cr2O7 used in titration, mL,
13.3.2 Sodium Diphenylamine Sulfonic Acid Indicator (2 B = 0.004 (Fe2O3 equivalent of K2Cr2O7), and
g/L)—Dissolve 0.20 g sodium diphenylamine sulfonate in 100 C = sample, g.
mL of water. Store in a dark-colored bottle. 13.6 Precision and Bias:
13.3.3 Mercuric Chloride Solution (5 %)—Dissolve 5 g of 13.6.1 Four laboratories cooperated in testing on four lime-
HgCl2 in 100 mL of water. stone samples and three laboratories cooperated in testing on
13.3.4 Potassium Dichromate, Standard Solution (0.05 an additional seven limestone samples thereby obtaining the
N)—Dry pure crystals of K2Cr2O7 at 110°C, then pulverize and precision data summarized in Table 3.
dry at 180°C to constant weight. Dissolve 2.4518 g of 13.6.2 The user is cautioned to verify by the use of reference
pulverized K2Cr2O7 in water and dilute to 1 L. This is a materials, if available, that the bias of this test method is
primary standard, 1 mL = 0.0040 g Fe2O3. adequate for the contemplated use.
9
C25 − 17
14. Total Iron by Ortho-Phenanthroline Photometric curve by plotting the absorbance versus the concentration of
Method Fe2O3 in µg/mL of solution.
14.1 Scope—When the iron oxide content is very low, less 14.4 Procedure:
than 0.1 %, and an accurate analysis at this low level is 14.4.1 Weigh 1 g of the properly prepared sample in 10 mL
required, it is preferable to determine iron using procedures HCl (1 + 1) and evaporate rapidly to dryness. Add 50 mL of
that have better sensitivity than the titrimetric methods. For an HCl (1 + 4) and heat to dissolve the salts. Filter the insoluble
accurate determination of minute amounts of iron, the ortho matter including SiO2 through a retentive paper and wash
phenanthroline method has proved invaluable.6 In general, the several times with hot water. Reserve the residue. Heat the
method consists of reducing the iron to the ferrous state and filtrate to boiling.
then adding a slight excess of 1, 10 phenanthroline, which 14.4.2 Place the paper containing the insoluble matter from
forms a complex with ferrous iron, giving an orange-pink the evaporated HCl solution in a platinum crucible. Char the
color. The color intensity is proportional to the iron content of paper at low heat without inflaming, then ignite at higher heat
the solution. until the carbon has been completely burned off. Cool, add
14.2 Summary of Test Method—The bulk of the iron in the 1 mL H2SO4 and 10 to 15 mL HF and evaporate to fumes of
sample is dissolved with HCl, the silica dehydrated and sulfuric acid. Cool, dilute the contents of the crucible with
separated by filtration, and the insoluble matter including SiO2, water, and warm to dissolve salts. Transfer the acidified
ignited in a platinum crucible and treated with HF and H2SO4 solution to the main solution containing the bulk of the iron.
to expel the SiO2 and recover the small amount of iron that 14.4.3 Transfer the combined solutions to a 100 mL volu-
may not have dissolved with HCl. The acidified solution is metric flask and dilute to volume. Pipet the aliquot containing
transferred to a volumetric flask and diluted to volume. The 0.02 to 0.10 mg Fe2O3 into a 50 mL volumetric flask. Dilute to
iron is reduced with hydroxylamine hydrochloride and the about 25 mL and add in the following sequence, mixing well
color of the ferrous complex is developed with 1,10 phenan- after each addition: 1 mL hydroxylamine hydrochloride, 5 mL
throline and compared against a set of iron standards similarly ammonium acetate, and 5 mL of 1,10 phenanthroline. Roll a
treated. small piece of congo red paper into a ball and insert into the
14.3 Special Solutions: volumetric flask. Add NH4OH (1 + 1) until the congo red
14.3.1 Hydroxylamine Hydrochloride (10 g/100)—Dissolve indicator turns a bright red, then add one drop of NH4OH
10 g of hydroxylamine hydrochloride in 100 mL of water. (1 + 1) in excess. Dilute to 50 mL, mix and let stand for 15 to
Prepare fresh every week. 20 min. Determine the absorbance of the solution in a
14.3.2 Ammonium Acetate (20 g/100)—Dissolve 200 g in spectrophotometer at a wavelength setting of 510 nm using
1 L of water. water in the reference cell. Compare against a set of standards
14.3.3 1,10 (Ortho) Phenanthroline (0.1 g/100)—Dissolve similarly treated.
1.0 g in 1 L of hot water. 14.5 Calculation:
14.3.4 Iron Standard Solution (1 mL = 1.0 mg Fe2O3)— 14.5.1 Calculate the % Fe2O3 as follows:
Dissolve 0.7000 g of pure iron wire by heating gently in 20 mL
C 3D
of HCl (1 + 1) and dilute to 1 L in a volumetric flask. % Fe2 O 3 5 (7)
W 3 104
14.3.4.1 Iron Work Standard Solution (1 mL = 0.01 mg
Fe2O3)—Transfer 10 mL of the iron standard solution to a 1 L where:
volumetric flask and dilute to volume with water. C = concentration of Fe2O3 in sample solution, µg/mL
14.3.5 Preparation of Calibration Curve—To each of six (determined from calibration curve),
50-mL volumetric flasks, add, respectively, 1, 2, 4, 6, 8, and 10 D = dilution factor, and
mL of working iron standard solution. When diluted to volume, W = sample mass, g.
each mL of the prepared standard solutions will contain,
14.6 Precision and Bias:
respectively 0.2, 0.4, 0.8, 1.2, 1.6, and 2.0 micrograms Fe2O3.
14.3.5.1 Add to each flask in the following sequence, 14.6.1 The number of laboratories, materials, and determi-
mixing after each addition, 1 mL of hydroxylamine hydrochlo- nations in this study does not meet the minimum requirements
ride solution, 5 mL of ammonium acetate, and 5 mL of 1,10 for determining precision prescribed in Practice E691:
phenanthroline. Roll a small piece of congo red paper into a Test Methods Practice E691
C25 Minimum
ball and insert it into the volumetric flask. Add NH4OH (1 + 1) Laboratories 2 6
until the congo red indicator turns bright red, then add 1 drop Materials 5 4
of NH4OH (1 + 1) in excess. Dilute to 50 mL, mix, and let Determinations 4 2
stand for 15 to 20 min. Determine the absorbance of the 14.6.2 The following precision statements are provisional.
solution in a spectrophotometer at a wavelength setting of Within five years, additional data will be obtained and pro-
510 nm using water in the reference cell. Prepare a calibration cessed which does meet the requirements of Practice E691.
14.6.2.1 Precision, characterized by repeatability, Sr and r,
6
Sandel, E. B., Colorimetric Determination of Traces of Metals, 3rd Ed., and reproducibility, SR and R, has been determined for the
Interscience Publications, 1959. following test method and materials to be:
10
C25 − 17
Precision Statement for 16.3.2 Ammonium Oxalate Wash Solution (1 g/L)—

% Fe2O3 Color
Test Method: Dissolve 1 g of (NH4)2C2O4 in 1 L of water.
Material Average Sr SR r R
S-1143 0.0358 0.0058 0.0201 0.0163 0.0564 16.4 Procedure:
S-1145 0.0480 0.0053 0.0214 0.0148 0.0599
S-1141 0.1688 0.0466 0.0640 0.1306 0.1792 16.4.1 Add 30 mL of HCl (1 + 1) and 20 mL of 10 % oxalic
S-1142 0.2025 0.0141 0.0631 0.0396 0.1767 acid to the combined filtrates from the iron and aluminum
S-1144 0.9252 0.0562 0.2096 0.1574 0.5870
hydroxide precipitation and heat the solution to boiling. To the
boiling solution, add ammonium hydroxide (1 + 3) slowly until
15. Aluminum Oxide
a precipitate begins to form. At this point, add the ammonium
15.1 Scope—Aluminum oxide, for the purpose of this test hydroxide still more slowly (dropwise, with a pipet) while
method, is considered to be the difference between the com- stirring continuously until the methyl red just turns yellow. Add
bined oxides and Fe2O3. When phosphorus or titanium are 25 mL of hot saturated ammonium oxalate solution while
determined, their oxides must also be deducted. stirring. Remove from the heat and let stand until the precipi-
15.2 Procedure—Subtract the percent Fe2O3 obtained in tate has settled and the supernatant liquid is clear. Allow to cool
accordance with Sections 5.1.1 and 5.1.2 from the percent for a minimum of 1 h, and filter using a retentive paper. Wash
combined oxides (see Section 5.1). Report the remainder as the paper and precipitate with five 10-mL portions of cold,
percent Al2O3. In special cases where P2O5 and TiO2 need to neutral 0.1 % solution of (NH4)2C2O4 (see Note 22). Reserve
be reported, a correction for these oxides must be made. filtrate for the magnesium determination.
15.3 Calculation—Calculate the percent Al2O3 as follows: NOTE 22—Hot solutions should be avoided when washing the CaC2O4
precipitate. One litre of hot water will dissolve 5 mg of CaO. One litre of
cold 0.1 % (NH4)2C2O4 solution will dissolve only 0.1 mg of CaO.
Al2 O 3 , % 5 A 2 B (8)
16.4.2 Place the wet filter and precipitate in a platinum
where: crucible, and char the paper without inflaming at low heat.
A = combined oxides (Al2O3 + Fe2O3), %, and Increase the heat to burn off all the carbon and ignite at 1000°C
B = Fe2O3, %. for about 10 min. Cool, dissolve the ignited oxide in 50 mL of
15.4 Precision and Bias: dilute HCl (1 + 4), and dilute to about 100 mL with water. Add
15.4.1 Four laboratories cooperated in testing on four lime- a few drops of methyl red indicator and neutralize with
stone samples and three laboratories cooperated in testing on NH4OH till the color of indicator changes to yellow. Heat just
an additional seven limestone samples thereby obtaining the to boiling. If a small amount of Al(OH)3 separates, filter it,
precision data summarized in Table 3. wash with a hot 2 % solution of NH4Cl, ignite, weigh, and add
15.4.2 The user is cautioned to verify by the use of reference this to the mass of Al2O3 determined in 15.2.
materials, if available, that the bias of this test method is 16.4.3 Heat the filtrate to boiling and add slowly, while
adequate for the contemplated use. stirring, 35 mL of saturated (NH4)2C2O4 solution. Digest, filter,
and wash as in 16.4.1. Combine the filtrate and washing with
16. Calcium Oxide by Gravimetric Method the ones reserved from the first precipitation, and retain for the
determination of MgO. Place the filter in a tared platinum
16.1 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. Increase the heat to burn off the carbon and ignite
determination of the ammonium hydroxide group. The precipi-
the calcium oxide in the covered platinum crucible at 1000°C.
tate is converted to CaO by ignition and weighed. The
Cool in a desiccator and weigh as CaO. 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.
gravimetric analysis is required.
16.2 Summary of Test Method—Calcium is precipitated with 16.5 Calculation—Calculate the percent calcium oxide
ammonium oxalate (NH4)2C2O4, filtered, ignited to the oxide, (CaO) as follows:
and redissolved with HCl. Any of the NH4OH group of metals
that escaped precipitation before may be recovered at this point CaO, % 5 ~ M/W ! 3 100 (9)
by the addition of a small amount of NH4OH and boiling. Any where:
precipitate that separates out is assumed to be Al(OH)3 and
after ignition to Al2O3 this amount is added to the mass of M = mass of CaO, g, and
W = mass of sample, g.
Al2O3 calculated in 16.2. Calcium is precipitated a second time
as the oxalate, filtered, washed, ignited, and weighed as CaO. 16.6 Precision and Bias:
16.3 Special Solutions: 16.6.1 Two laboratories cooperated in testing on four lime-
16.3.1 Ammonium Oxalate Solution (saturated)—Dissolve stone samples and obtained the precision data summarized in
45 g of ammonium oxalate (NH4C2O4) in 1 L of hot water. Table 3.
When cooled to room temperature the supersaturated solution 16.6.2 The user is cautioned to verify by the use of reference
will partially crystallize out and the supernatant solution will materials, if available, that the bias of this test method is
then be saturated with ammonium oxalate. adequate for the contemplated use.
11
C25 − 17
17. Calcium Oxide by Volumetric Method 17.4.1 Add 30 mL of HCl (1 + 1) and 20 mL of 10 % oxalic
17.1 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, but it is capable hydroxide precipitation and heat the solution to boiling. To the
of giving exact results, especially with those products that are boiling solution, add ammonium hydroxide (1 + 3) slowly until
free of interfering elements. Traces of strontium, barium, a precipitate begins to form. At this point, add the ammonium
magnesium, or oxalate that may be present will also be titrated hydroxide still more slowly (dropwise, with a pipet) while
and calculated as calcium on an equivalence, not weight, basis. stirring continuously until the methyl red just turns yellow. Add
25 mL of hot saturated ammonium oxalate while stirring.
17.2 Summary of Test Method—In this test method, 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. Allow to cool and
acid and the liberated oxalic acid is titrated with standard filter at the end of 1 h. Wash the paper with cold water, limiting
potassium permanganate. The calcium equivalent of the oxalic the total washings to 125 mL (see Note 23). Retain the filtrate
acid is determined and the grams of CaO calculated. for magnesium.
NOTE 23—A Gooch crucible may be used instead of filter paper to filter
17.3.1 Potassium Permanganate, Standard Solution the CaC2O4 precipitate.
(0.175 N):
17.3.1.1 Dissolve 5.64 g of potassium permanganate 17.4.2 With a jet of hot water, wash the precipitate from the
(KMnO4) in 1 L of water and boil gently for 20 to 30 min. paper into the beaker in which the precipitation was made. Fold
Dilute again to 1 L, cover and allow to age for several days. the paper and leave it adhering to the upper portion of the
Filter through purified asbestos or a wad of glass wool, and beaker. Add to the contents of the beaker 250 mL of hot,
standardize against the National Institute of Standards and diluted H2SO4 (1 + 19) and heat to 80 to 90°C.
Technology’s standard sample 40C of sodium oxalate 17.4.3 Titrate with 0.175 N KMnO4 solution until the pink
(Na2C2O4) or equivalent as follows: end point is obtained. Drop the folded filter paper that
17.3.1.2 Transfer 0.5 g of the standard sodium oxalate dried contained the original precipitate into the liquid and macerate
at 105°C to a 400-mL beaker. Add 250 mL of diluted H2SO4 it with a stirring rod; the pink color of the solution will be
(5 + 95) freshly boiled for 10 to 15 min and cooled to discharged (see Note 24). Finish the titration by adding the
27 6 3°C. Stir until the oxalate has dissolved. Add 40 to 42 mL KMnO4 standard solution dropwise until the end point is again
of the standard KMnO4 solution at the rate of 25 to 35 mL/min, obtained.
while stirring slowly. Let stand until the pink color disappears
NOTE 24—There will always be some fine particles of precipitate
(about 60 s) (see Note X1.2). imbedded in the pores of the filter paper which are dissolved by the acid
17.3.1.3 Heat the contents of the beaker to 60°C and in solution. The filter paper is not introduced at the beginning of the
complete the titration at this temperature by adding KMnO4 titration to avoid introduction of traces of organic matter due to the action
solution until a slight pink color persists for 30 s. Add the last of the hot sulfuric acid on the paper; these would consume KMnO4 and
0.5 to 1 mL dropwise, allowing each drop to become decolor- give high results for CaO.
ized before the next one is added. 17.5 Calculation—Calculate the percentage of CaO in the
17.3.1.4 Determine the exact normality of the KMnO4 sample using the CaO equivalent from 17.3.1.5 as follows:
solution from the following:
CaO, % 5 ~ V 3 F ! /W 3 100 (12)
N 5 W/V 3 0.06701 (10)
where:
where: V = KMnO4 solution used in titration, mL,
N = normality of KMnO4 solution, F = CaO equivalent of KMnO4, and
W = mass of standard sodium oxalate, W = original mass of sample, g.
V = KMnO4 used to titrate sodium oxalate, mL, and
0.06701 = sodium oxalate equivalent to 1 mL of 1 N KMnO4 17.6 Precision and Bias:
solution, g. 17.6.1 Two laboratories cooperated in testing on twelve
limestone samples and obtained the precision data summarized
17.3.1.5 Determine the CaO equivalent of the KMnO4
in Table 3.
solution as follows:
17.6.2 The user is cautioned to verify by the use of reference
materials, if available, that the bias of this test method is
F 5 N 3 0.02804 (11)
adequate for the contemplated use.
where:
F = CaO equivalent of the KMnO4 solution in grams 18. Magnesium Oxide
CaO/mL, 18.1 Scope—Magnesium oxide in lime and limestone may
N = normality of KMnO4 solution, and vary from a few tenths to 2 % for high-calcium limestone to as
0.02804 = CaO equivalent to 1 mL of 1 N KMnO4 solution, much as 22 % for dolomitic limestone. The pyrophosphate
g. gravimetric method has been used successfully throughout the
17.4 Procedure: industry to determine magnesium within this wide range.
12
C25 − 17
18.2 Summary of Test Method—In this test method, magne- on an additional nine limestone samples thereby obtaining the
sium is doubly precipitated as magnesium ammonium phos- precision data summarized in Table 3.
phate from the filtrate after removal of calcium. The precipitate 18.6.2 The user is cautioned to verify by the use of reference
is ignited and weighed as magnesium pyrophosphate materials, if available, that the bias of this test method is
(Mg2P2O7). The MgO equivalent is then calculated. adequate for the contemplated use.
18.3.1 Ammonium Phosphate, Dibasic Solution (250 g/L)— 19. Loss on Ignition
Dissolve 250 g of dibasic ammonium phosphate 19.1 Scope—Loss on ignition (LOI) is the loss in weight
((NH4)2HPO4) in 1 L of water. expressed as percent of the initial “as received” sample weight
18.3.2 Ammonium Hydroxide Wash Solution (5 + 95)— obtained after ignition of the sample at 1000°C to constant
Dilute 50 mL of NH4OH with 950 mL of water and add 1 or weight. The loss in weight is due to a release of free moisture,
2 mL of HNO3. chemically combined “lattice” or “hydroxy” water, CO2, SO2,
18.4 Procedure: and volatile pyrolytic products of any organic material that
18.4.1 Add 2 drops of methyl red indicator to the combined may be present.
filtrates from the determination of calcium, acidify with HCl, 19.2 Summary of Test Method—The tared crucible contain-
and concentrate to about 250 mL. Add to this solution about ing the weighed sample is ignited to constant weight. The loss
10 mL of the (NH4)2HPO4 solution, 250 g/L, and cool the in weight is the LOI of the sample.
solution to room temperature. Add NH4OH slowly while
stirring constantly until the solution is alkaline or the crystal- 19.3 Procedure—Transfer approximately 1 g of the sample
line magnesium ammonium phosphate begins to form; then prepared to pass a 100-mesh (149-µm) U.S. standard sieve to a
add about 15 to 20 mL of NH4OH in excess and continue tare-weighed porcelain or platinum crucible. Cover with a lid
stirring for several more minutes. Allow the beaker and and weigh accurately to within 0.1 mg. When testing
precipitate to stand in a cool place overnight. Filter and wash quicklime, the crucible cover is not required. Also, quicklime
with cold dilute ammonium hydroxide wash solution (5 + 95). may be placed directly into a muffle at 1000°C avoiding
18.4.2 Dissolve the precipitate with hot diluted HCl (1 + 9) preignition. Pre-ignite in a muffle furnace at approximately
and wash the filter paper well with hot diluted HCl (1 + 99). 400°C for 30 min. Then increase muffle temperature to
Dilute the solution to 100 mL, cool to room temperature, and 1000 6 20°C, and maintain at this temperature for a minimum
add 1 mL of the 20 % solution of (NH4)2HPO4. Precipitate the of 20 min or until constant mass is obtained. The difference
magnesium ammonium phosphate as before and allow to stand between the original mass of the sample and the final mass
for about 2 h in a cool place. represents the loss on ignition.
18.4.3 Filter the precipitate on paper or in a tared Gooch 19.4 Calculation—Calculate LOI as follows:
crucible, washing with diluted NH4OH (5 + 95). If filtered
through a Gooch, place directly in a muffle at 400°C and raise
LOI, % 5 ~ A 2 B ! /C 3 100 (14)
heat to 1100°C. If filtration was through paper, place paper and
precipitate in a weighed platinum or porcelain crucible. Slowly where:
char the paper without inflaming and carefully burn off the A = mass of crucible + sample, g,
resulting carbon (Warning—Extreme caution should be exer- B = mass of crucible plus sample after ignition, g, and
cised during this ignition. Reduction of the phosphate precipi- C = mass of sample, g.
tate can result if carbon is in contact with it at high tempera-
19.5 Precision and Bias (Limestone):
tures. There is also a danger of occluding carbon in the
precipitate if ignition is too rapid.). Ignite at 1100°C for 1⁄2 h, 19.5.1 Fifteen laboratories cooperated in testing on three
cool in desiccator, and weigh as Mg2P2O7 (see Note 25). samples of high calcium limestone to obtain the precision data
for percent LOI given in 19.5.2 and 19.5.3.
NOTE 25—For research purposes or in the most exacting types of work, 19.5.2 The repeatability (Practice E691 [r]) was found to be
the manganese content of the pyrophosphate residue should be determined
and deducted as Mn2P2O7. 0.158 % LOI.
19.5.3 The reproducibility (Practice E691 [R]) was found to
18.5 Calculation—Calculate the percentage of MgO to the
be 0.463 % LOI.
nearest 0.01 % as follows:
MgO, % 5 A 3 36.2/B (13) adequate for the contemplated use.
where: 19.6 Precision and Bias (Lime):
A = Mg2P2O7, g, 19.6.1 The precision of this test method is based on an
B = sample, g, and interlaboratory study conducted in 2008. Up to ten laboratories
36.2 = molecular ratio of 2MgO to Mg2P2O7 × 100.
tested a total of four alloys in three types of crucibles. Every
18.6 Precision and Bias: test result represents an individual determination. Each labo-
18.6.1 Four laboratories cooperated in testing on three ratory reported up to three replicate test results for the analysis.
limestone samples and three laboratories cooperated in testing Except for the number of reporting laboratories in some cases,
13
C25 − 17
Practice E691 was followed for the design and analysis of the (also known as “free-moisture”) is accepted; that is, the amount
data; the details are given in RR:C07-1008.7 of water and any other volatile matter than can be expelled
19.6.2 Repeatability Limit, 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.
differ by more than the r value for that material; r is the interval 20.2 Summary of Test Method—The sample in a container is
representing the critical difference between two test results for heated in a drying oven at 115 to 120°C constant weight. The
the same material, obtained by the same operator using the loss in weight represents the free moisture.
same equipment on the same day in the same laboratory.
19.6.2.1 Repeatability limits are listed in Table 4. 20.3 Special Apparatus:
19.6.3 Reproducibility Limit, R—Two test results shall be 20.3.1 Bottle, weighing, low-form, glass-stoppered, or
judged not equivalent if they differ by more than the R value wide-form, large porcelain crucible.
for that material; R is the interval representing the critical 20.4 Procedure—Weigh 1 g of the prepared sample in the
difference between two test results for the same material, stoppered weighing bottle. 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. Quickly stopper, cool in
different laboratories. a desiccator, and weigh, lifting the stopper momentarily just
19.6.3.1 Reproducibility limits are listed in Table 4. before weighing. The use of a similar weighing bottle as a
19.6.4 The terms repeatability limit and reproducibility limit counterpoise carried through all the operations is a desirable
are used as specified in Practice E177. procedure unless a single pan balance is used. The loss in
19.6.5 Any judgment in accordance with statements 19.6.2 weight represents “free moisture” loss at 120°C.
and 19.6.3 would normally have an approximate 95% prob- 20.5 Calculation—Calculate the percent “free moisture” as
ability of being correct, however the precision statistics ob- follows:
tained in this ILS must not be treated as exact mathematical
quantities which are applicable to all circumstances and uses. Free moisture, % 5 ~ A 2 B ! /C 3 100 (15)
The limited number of laboratories reporting replicate results where:
using the platinum crucibles guarantees that there will be times A = mass of crucible and sample before heating, g,
when differences greater than predicted by the ILS results will B = mass of crucible and sample after heating at 120°C, g,
arise, sometimes with considerably greater or smaller fre- and
quency than the 95% probability limit would imply. The C = original mass of sample, g.
repeatability limit and the reproducibility limit, at least as
concerns the platinum crucible data, should be considered 20.6 Precision and Bias—The precision and bias of this test
general guides, and the associated probability of 95% as only method have not been determined.
a rough indicator of what can be expected. 21. Free Moisture in Hydrated Lime
19.7 Bias—At the time of the study, there was no accepted 21.1 Scope—The free moisture in hydrated lime is that
reference material suitable for determining the bias for this test water that is released from the sample at relatively low drying
method, therefore no statement on bias is being made. temperatures. This distinguishes it from the hydroxyl water
19.8 The precision statement was determined through sta- that is chemically bound to the lime and which cannot be
tistical examination of 252 results, from ten laboratories, on liberated except at higher temperatures. Two test method
four materials which are described below: options are described for determination of free moisture in
Hi-Cal Lime # 1: High Calcium Lime hydrated lime.
Hi-Cal Lime #2: High Calcium Lime
21.2 Purifying Gas Train Test Method—Free moisture in
Do Lime #2: Dolomitic Lime
Do Lime #1: Dolomitic Lime hydrated lime is determined by aspirating a slow stream of
CO2-free air over the sample in a container placed inside a 115
20. Free Moisture in Limestone to 120°C oven. The loss in mass of the sample is equal to the
20.1 Scope—For the purpose of this test method, the con- free moisture of the hydrated lime.
ventional definition of “hygroscopic moisture” or “free water” 21.2.1 Special Apparatus:
21.2.1.1 Sample Flask E, illustrated in Fig. 1, consists of a
7
Supporting data have been filed at ASTM International Headquarters and may 50-mL flat-bottom, glass-stoppered flask, supplied with a
be obtained by requesting Research Report RR:C07-1008. ground glass joint and solid ground glass stopper.
TABLE 4 Loss on Ignition Results for Lime Using Platinum, Porcelain, and Quartz Crucibles Combined (%)A
Repeatability Reproducibility
Average,B Repeatability Reproducibility
Material Standard Standard
x̄ Limit, r Limit, R
Deviation, Sr Deviation, SR
Hi-Cal Lime # 1 0.796 0.056 0.113 0.158 0.316
Hi-Cal Lime #2 2.275 0.204 0.315 0.572 0.883
Do Lime #2 2.460 0.190 0.278 0.532 0.779
Do Lime #1 0.748 0.096 0.157 0.270 0.440
A
Statistics based on results from 10 laboratories.
B
The average of the laboratories’ calculated averages.
14
C25 − 17
A Soda-Lime Tower at inlet to remove CO2.

B Bottle containing lime water to show when soda lime tower is exhausted.
C Fleming jar containing sulfuric acid to remove water from air.
D Absorption bulb filled with Anhydrone (Magnesium Perchlorate) to complete drying of air.
E 50-mL sample flask.
F Drying oven operating at 110°C.
G Absorption bulb filled with Anhydrone to prevent moisture backup into sample.
FIG. 1 Apparatus for Free Moisture in Hydrated Lime
(1) The flask shall be fitted with an interchangeable hollow 21.2.3 Calculation—Calculate the percent “free moisture”
ground-glass stopper, equipped with two glass entry tubes for in the sample as follows:
conducting the dry air over the sample.
21.2.1.2 Purifying Train (see Fig. 1), located outside the Free moisture, % 5 ~ A 2 B ! /C 3 100 (16)
oven for conducting the dry air over the samples, shall consist
of a series of scrubbers and absorption bulbs to remove CO2 where:
and moisture from the air. The apparatus are arranged in the A = mass of sample flask + sample, g,
following order starting from the air source: B = mass of sample flask after drying, g, and
(1) Soda-lime Tower A, at the air inlet to remove CO2 from C = initial mass of sample, g.
the air. 21.2.4 Precision and Bias—The precision and bias of this
(2) Bottle B, containing lime water to show when the soda test method have not been determined.
lime is exhausted.
(3) Fleming Jar C, containing sulfuric acid to remove 21.3 Moisture Test Method—Free moisture in hydrated lime
water from the air. is determined by heating the sample to a constant temperature
(4) Absorption Bulb D, filled with Anhydrone (magnesium between 150 and 180°C on a sample pan that is supported on
perchlorate) to complete the drying of the air. a balance. The loss in mass of the sample is equal to the free
(5) Sample Flask E. moisture of the hydrated lime.
(6) Drying Oven F. 21.3.1 Special Apparatus:
(7) Absorption Bulb G, also filled with Anhydrone and 21.3.1.1 Moisture Analyzer, consisting of:
located on the exit side of the sample bulb as a protective (1) An integrated heat source capable of heating the sample
barrier against atmospheric moisture. to at least 150°C and calibrated using NIST traceable tempera-
21.2.2 Procedure—Weigh 2.5 to 3 g of the prepared sample ture calibration interface.
and record the mass. Using glazed paper folded in the shape of (2) A balance capable of measuring to 0.001 g and cali-
a funnel, transfer the weighed sample rapidly into the previ- brated using NIST traceable weights.
ously weighed flask and immediately restopper it. Insert the (3) Automatic endpoint, mass change <0.1 % over 60 s can
flask into the 115 to 120°C oven and quickly exchange be programmed.
stoppers. Connect the sample flask to the purifying train by (4) Electronics capable of compensating for lift caused by
means of flexible tubing and pass a slow current of dry convection currents created during testing and for converting
CO2-free air through the apparatus for 2 h. Disconnect the loss of mass to digital data.
sample flask from the train, remove it from the oven with (5) Digital display for presenting the digital data as percent
another quick exchange of stoppers, and place it in a desiccator moisture.
to cool. When cool, remove it to the balance case for several
NOTE 26—These analyzers are also called moisture balances.
minutes before weighing it, and just before weighing, lift the
stopper slightly for an instant to relieve any vacuum that may 21.3.1.2 Sample Pans, made from “0” temper, Aluminum
exist in the flask. Record the mass of the flask plus the dried 3003 or other nonreactive material.
sample. The loss in mass of the sample represents “free 21.3.2 Calibration and Validation:
moisture” loss. Use a flask similar to the one containing the 21.3.2.1 To maintain the integrity of the test results the
sample as a counterpoise in all weighings unless a single-pan balance and heater shall be capable of being calibrated using
balance is used. NIST traceable sources.
15
C25 − 17
21.3.2.2 The accuracy of the analyzer is validated by using 21.3.5.2 Reproducibility (R)—The difference between two
ACS Reagent Grade Sodium Tartrate Dihydrate at multiple single and independent results obtained by different operators
masses to show linearity. applying the same test method in different laboratories using
21.3.3 Procedure: different apparatus on identical test material would, in the long
21.3.3.1 Turn the analyzer on and allow it to equilibrate for run, in the normal and correct operation of the test method,
a minimum of 15 minutes. Program the analyzer for the exceed the following values only in one case in 20.
following test conditions: (1) Reproducibility can be interpreted as the maximum
Idle Temperature: 50°C difference between two results, obtained under reproducibility
Test Temperature: A minimum of 150°C and not to exceed conditions that are accepted as plausible due to random causes
180°C
End Point: Mass change <0.1 % over 60 s
under normal and correct operation of the test method.
(2) Reproducibility limits are listed in Table 5.
21.3.3.2 Spread 5.0 6 0.5 g of hydrated lime evenly over
the surface of the sample plan. A larger sample mass may be NOTE 27—C07 is working on additional materials in order to complete
required based on manufacturer recommendations. the Precision and Bias statement for this method.
21.3.3.3 Follow the procedure indicated on the display 21.3.5.3 Bias—At the time of the study, there was no
panel of the analyzer. accepted hydrated lime reference material suitable for deter-
21.3.4 Calculation—Results will be displayed on the ana- mining the bias for this test method, therefore no statement on
lyzer so no calculation is necessary, or if the mass is recorded: bias is being made.
Free Moisture, % 5 ~ A 2 B ! ⁄A 3 100 (17) 22. Carbon Dioxide by Standard Method
where: 22.1 Scope—Carbon dioxide in limestone is sometimes
A = initial mass of sample, and determined to verify the presence of carbonates other than
B = mass of sample at endpoint. calcium or magnesium. These may include carbonates of iron,
manganese, and occasionally traces of other substances.
21.3.5 Precision and Bias—he precision of this test method
Samples of lime and hydrated lime are analyzed for CO2 to
is based on an interlaboratory study conducted to support C25,
check for the presence of carbonates, most of which are there
Standard Test Methods for Chemical Analysis of Limestone,
as uncalcined limestone.
Quicklime, and Hydrated Lime, conducted in 2014. Eleven
laboratories participated in this study. Each of the eleven labs 22.2 Summary of Test Method—The sample is decomposed
reported three replicates of two different hydrated lime mate- with HCl and the liberated CO2 is passed through a series of
rials as well as three replicates of a reference material. Every scrubbers to remove water and sulfides. The CO2 is absorbed
“test result” reported represents an individual determination. with Ascarite, a special sodium hydroxide absorbent, and the
Practice E691 was followed for the design and analysis of the gain in weight of the absorbtion tube is determined and
data; the details are given in ASTM Research Report No. calculated as percent CO2.
C07-XXXX.8 22.3 Special Apparatus:
21.3.5.1 Repeatability (r)—The difference between repeti- 22.3.1 The apparatus illustrated in Fig. 2 consists of the
tive results obtained by the same operator in a given laboratory following:
applying the same test method with the same apparatus under 22.3.1.1 Purifying Jar A, Fleming, containing sulfuric acid.
constant operating conditions on identical test material within 22.3.1.2 Drying Tube B, U-shaped with side arms and glass
short intervals of time would in the long run, in the normal and stoppers. Side arms are shaped to hold rubber tubing. Contains
correct operation of the test method, exceed the following Anhydrone on left side and Ascarite on right side.
values only in one case in 20. 22.3.1.3 Erlenmeyer Flask C, 250-mL, 24/40 ground-glass
(1) Repeatability can be interpreted as the maximum dif- joint.
ference between two results, obtained under repeatability 22.3.1.4 Separatory Funnel D, with ground-glass stopper
conditions that are accepted as plausible due to random causes and interchangeable hollow ground-glass joint. A delivery tube
under normal and correct operation of the test method. bent at the end extends into the sample flask about 1⁄2 in. from
(2) Repeatability limits are listed in Table 5. the bottom. Used to introduce acid into flask.
22.3.1.5 Condenser E.
22.3.1.6 Gas-Washing Bottle F, 250-mL, with fritted disk
8
Supporting data have been filed at ASTM International Headquarters and may containing distilled water to retain most of the acid volatilized
be obtained by requesting Research Report RR:XXX-XXX. Contact ASTM
Customer Service at service@astm.org. from the alkalimeter.
TABLE 5 Test Result (Wt%)

Repeatability Reproducibility
Average,A Repeatability Reproducibility
Material Standard Deviation, Standard
x̄ Limitm r Limitm R
Sr Deviationm SR
ACS Reagent Grade Sodium Tartrate Dihydrate 15.709 0.046 0.157 0.129 0.439
Sample A Hydrated Lime 1.108 0.032 0.176 0.090 0.493
Sample B Hydrated Lime 0.905 0.030 0.212 0.083 0.594
A
The average of the laboratories’ calculated averages.
16
C25 − 17
A Purifying jar, Fleming, containing concentrated H2SO4.

B Drying tube, U-shaped, Ascarite in right side, Anhydrone in left side.
C Erlenmeyer flask, 250-mL, 24/40 glass joint.
D Separatory funnel.
E Condenser.
F Gas-washing bottle, 250-mL with fritted disk, containing water to retain most of the acid volatilized from the alkalimeter.
G U-tube containing mossy zinc to remove the last traces of HCl.
H Gas-washing bottle, 250-mL with fritted disk, containing concentrated H2SO4.
I Trap.
J Absorption bulb containing Anydrone.
K CO2 absorption bulb containing Ascarite.
L U-guard tube with Anhydrone in left side and Ascarite in right side.
M Purifying jar, Fleming, containing concentrated H2SO4.
FIG. 2 Apparatus for Carbon Dioxide by Standard Method
22.3.1.7 U-Tube G, containing mossy zinc to remove the the stopcock of the separatory funnel and admit air through the
last traces of HCl. top of the funnel to force the hydrochloric acid into the
22.3.1.8 Gas-Washing Bottle H, 250-mL, with fritted disk, Erlenmeyer flask (C).
containing concentrated H2SO4 and trap I, to remove any SO3 22.4.3 Start cold water circulating through the condenser
mist that may have been carried over. (E) and, with CO2-free air passing at a moderate rate through
22.3.1.9 Absorption Bulb J, containing Anhydrone to re- the absorption train, place a small hot plate or gas burner under
move last traces of water vapor. the sample flask and boil for about 2 min. Remove the hot plate
22.3.1.10 CO2 Absorption Bulb, containing Ascarite filled and continue the flow of purified air at about three bubbles per
as follows: On the bottom of the bulb, place a layer of glass second for 30 min to sweep the apparatus free of CO2. Close
wool extending above the bottom outlet and on top of this a the absorption bulb, disconnect it from the train and weigh,
layer of Anhydrone about 3⁄8 in. thick; immediately above this opening the stopper momentarily to equalize the pressure. Use
is placed another layer of glass wool, and Ascarite is then a second absorption bulb as counterpoise in all weighings
added to almost fill the bulb. A top layer of Anhydrone about unless a single pan balance is used.
3⁄8 in. thick is placed on top of the Ascarite and topped off with
22.5 Calculation—Calculate the percent CO2 as follows:
a covering of glass wool.
22.3.1.11 U-Guard Tube L, filled with Anhydrone in left
side and Ascarite in right side. CO2 , % 5 ~ A 2 B ! /C 3 100 (18)
22.3.1.12 Purifying Jar M, Fleming, containing H2SO4. where:
22.4 Procedure: A = mass of absorption bulb + CO2, g,
22.4.1 Weigh an indicated amount of prepared sample, 0.5 g B = mass of absorption bulb before the run, g, and
for limestone and 5 g for lime or hydrated lime, and transfer to C = mass of sample, g.
the 250-mL Erlenmeyer flask. Connect the sample flask to 22.6 Precision and Bias—The precision and bias of this test
apparatus as shown in the diagram (see Fig. 2). Purge the method have not been determined.
system free of carbon dioxide by passing a current of CO2-free
air through the apparatus for 10 to 15 min. 23. Sulfur Trioxide
22.4.2 Weigh the absorption bulb and attach it to the train. 23.1 Scope—This test method will determine sulfur
Remove the glass stopper from separatory funnel, place 50 mL compounds, mostly present as sulfates in lime and limestone,
of dilute HCl (1 + 1) in the separatory funnel (D) and replace that are soluble in dilute HCl. Iron pyrites and other sulfides
the stopper with the interchangeable hollow ground-glass joint will not be included because they will either be volatilized as
through which passes a tube for admitting purified air. Open H2S or not react at all with the acid.
17
C25 − 17
23.2 Summary of Test Method—In this test method, 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, the difference can be assumed to be present as
with barium chloride (BaCl2) and the SO3 equivalent is iron disulfide.
calculated. 24.2 Summary of Test Method—The sample is fused with
23.3 Special Solution: sodium carbonate and the ignited mass is leached in water and
23.3.1 Barium Chloride Solution (100 g/L)—Dissolve dissolved with HCl. The solution is made ammoniacal and the
100 g of barium chloride (BaCl2 · 2H2O) in 1 L of water. hydroxide precipitate is filtered. The sulfur in the filtrate is
precipitated with a 10 % solution of barium chloride. The
23.4 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.
with the following:
24.3 Procedure:
Expected SO3 Range, % Sample Weight, g
0.001 to 0.500 10.00
24.3.1 Select and weigh the prepared sample into a porce-
0.500 to 2.50 5.00 lain crucible in accordance with the following:
2.50 to 12.5 2.00
Expected S Range, % Sample Weight, g Na2CO3 Weight, g
Stir until all lumps are broken and the lighter particles are in 0.001 to 0.20 10.00 5.00
0.200 to 1.00 5.00 2.50
suspension. Add 50 mL of diluted HCl (1 + 1) and heat until 1.00 to 5.00 2.00 1.00
the reaction has stopped and decomposition is complete. Digest
Add the indicated amount of Na2CO3 and mix well. Heat in
for several minutes at a temperature just below boiling. Add a
a muffle at 600°C for 15 min. 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). Heat the solution
for 15 min. (see Note 28). Cool, place the crucible and cover in
to boiling. Filter through a medium-textured paper and wash
a 400-mL beaker, and cover with hot water. Add 10 mL
the residue thoroughly with hot water. Dilute the filtrate to
bromine water (see Note 29) and then add sufficient HCl
250 mL, add 5 mL of HCl (1 + 1), heat to boiling, and add
(1 + 1) to make the solution slightly acid to methyl red. Boil
slowly 10 mL of hot BaCl2 solution. Continue the boiling until
until solution is complete and all bromine has been expelled.
the precipitate is well formed, stir well, and allow to stand
Remove the crucible and wash with hot water.
overnight at room temperature. Take care to keep the volume of
solution between 225 and 250 mL, and add water for this NOTE 28—Since not enough flux is used to produce more than a
purpose if necessary. Filter through a retentive paper and wash sintering, the air entering the crucible after the bulk of the carbon dioxide
has been released effects very speedy oxidation in the porous mass.
the precipitate with hot water. Place the paper and contents in
NOTE 29—It has been found that 10 mL of 30 % hydrogen peroxide
a weighed platinum crucible, and slowly char the paper without (H2O2) may be substituted for the bromine water to accomplish oxidation
flaming. Burn off all the carbon, ignite in a muffle at 1000°C, without affecting the analytical result.
cool in a desiccator, and weigh. 24.3.2 Add a few drops of methyl red indicator and render
23.5 Calculation—Calculate the percentage of SO3 to the the solution alkaline with NH4OH (1 + 1). Heat the solution to
nearest 0.001 as follows: boiling, filter using a retentive paper and wash with hot water.
SO3 , % 5 A 3 0.343/W 3 100 (19)
To the filtrate add 5 mL of HCl (1 + 1), adjust the volume to
about 250 mL, and bring the solution to boiling. To the boiling
where: solution, add 10 mL of hot BaCl2 solution, slowly and with
A = mass of BaSO4, g, stirring. Allow to stand overnight. Filter through a retentive
W = mass of sample, g, and paper and wash the precipitate with hot water. Place paper and
0.343 = molecular ratio of SO3 to BaSO4. contents in a weighed platinum crucible and slowly char the
paper without flaming. Burn off the carbon and ignite in a
muffle at 1000°C for 1 h. Cool in a desiccator and weigh as
23.6.1 Six laboratories cooperated in testing on four BaSO4.
samples of limestone and lime materials covering the range
from 0.04 to 5.15 % SO3 to obtain the precision data given in 24.4 Calculation—Calculate the percentage of sulfur to the
23.6.2 and 23.6.3. nearest 0.001 as follows:
23.6.2 The repeatability (Practice E173 R1) was found to be
(0.135 % SO3 per weight in grams of sample analyzed). S, % 5 A 3 13.73/W (20)
23.6.3 The reproducibility (Practice E173 R2) was found to where:
be (0.271 % SO3 per weight in grams of sample analyzed). A = mass of BaSO4, g,
23.6.4 The user is cautioned to verify by the use of reference W = sample, g, and
materials, if available, that the bias of this test method is 13.73 = mass of molecular ratio of S to BaSO4 × 100.
24.5.1 Six laboratories cooperated in testing on four
24. Total Sulfur by Sodium Carbonate Fusion
samples of limestone and lime materials covering the range
24.1 Scope—Sulfur in limestone is chiefly, if not wholly, from 0.021 to 2.15 % sulfur to obtain the precision data given
present as sulfide, usually as pyrite. If the total sulfur obtained in 24.5.2 and 24.5.3.
18
C25 − 17
24.5.2 The repeatability (Practice E173 R1) was found to be as possible. The crucibles for use in the induction furnace must
(0.065 % S per weight in grams of sample analyzed). have adequate capacity and may be provided with suitable
24.5.3 The reproducibility (Practice E173 R2) was found to covers.
be (0.094 % S per weight in grams of sample analyzed). 25.3.5 Glass Accelerator Scoop.
24.5.4 The user is cautioned to verify by the use of reference 25.3.6 Starch Dispenser—A plastic bottle with a device for
materials, if available, that the bias of this test method is dispensing a few millilitres of starch solution at a time.
adequate for the contemplated use. 25.3.7 Timer, having a 0 to 15-min range in 1⁄4-min intervals.
Turns off the furnace at end of preset time and automatically
25. Total Sulfur by the Combustion-Iodate Titration resets.
Method 25.3.8 Loading Funnel—Three-legged funnel that fits over
the crucible and simplifies addition of sample.
25.1 Scope—This test method covers the determination of
sulfur in concentration from 0.005 to 1 %. At the combustion 25.4 Reagents:
temperature of approximately 1650°C, complete combustion of 25.4.1 Copper (Low-Sulfur) Ring Accelerator.
the sulfur in the sample will take place regardless of sulfur 25.4.2 Iron (Low-Sulfur) Accelerator—Iron chips. (For
form or sample matrix. samples containing very low percentages of sulfur, the use of
iron powder is recommended because of its low blank.)
25.2 Summary of Test Method—A major portion of the 25.4.3 Tin Metal (Low-Sulfur) Accelerator, granular.
sulfur in various types of lime and limestone samples is 25.4.4 Potassium Iodate (KIO3) Crystal.
converted to oxides of sulfur, primarily sulfur dioxide (SO2), 25.4.5 Potassium Iodide (KI) Crystal.
by combustion in a stream of oxygen at the elevated tempera-
25.4.6 Starch, soluble.
ture of a high-frequency induction furnace. During the
combustion, the SO2 is absorbed in an acidified starch-iodine 25.5 Special Solutions:
solution and titrated with potassium iodate. The latter is 25.5.1 Potassium Iodate, standard solutions.
standardized against limestone standard samples of known 25.5.1.1 KIO3 Standard Solution A—Dissolve 0.2227 g
sulfur content to compensate for characteristics of a given KIO3 in 900 mL of water containing 1 g sodium hydroxide
apparatus and for day-to-day variation in the percentage of (NaOH) and dilute to 1 L. For a 0.500-g sample, the buret reads
sulfur recovered as SO2. Compensation is also made for the directly in percent sulfur.
blank due to accelerators and crucibles. 25.5.1.2 Starch-Iodide Solution—Transfer 2 g of soluble
starch (for example, Arrowroot) to a 50-mL beaker, add a few
25.3 Apparatus:
millilitres of water, and stir into a smooth paste. Slowly add
25.3.1 Induction Furnace—The induction furnace shall be starch to 500 mL of distilled water while stirring. Add 4 g of
supplied with a rheostat used to control the power input to the NaOH and continue stirring the solution until the appearance
reduction coil that will avoid heating some types of samples changes from cloudy to translucent. Add 6 g of potassium
too rapidly during the early stages of combustion. The train of iodide (KI), stir until the KI is dissolved, and dilute to 1 L.
the induction furnace shall include an oxygen purifier, de-
scribed in 25.3.3. NOTE 30—Discard any starch solution that imparts a red tinge to the
blue color when titrating.
25.3.2 Automatic Titrator—This apparatus shall consist of
an absorption and titration vessel of appropriate volume and 25.6 Calibration—This test method and instrument should
contain an inlet bubbler tube for the sulfur gases with a float be standardized by using a limestone sample of known sulfur
valve to prevent backflow of liquid when the sample is starting content as determined by the Total Sulfur Method by Sodium
to consume oxygen. The vessel must be shaped to effect Carbonate Fusion, Section 24. The Leco instrument, in
complete absorption of SO2 in a small volume of solution. The addition, may be standardized daily by running limestone
titrator comes equipped with a buret that should be approxi- reference materials whose sulfur content, as determined by the
mately 10 mL in capacity marked with 200 divisions. The Total Sulfur Method, ranges from 0.02 to 0.05 %. The lime-
automatic titrator utilizes a photoelectric cell to activate a stone standards are run to determine the day-to-day variations
titrator inlet valve that allows the titration to proceed without in the test method and to verify that the electronics in the Leco
the presence of an operator. are working properly.
25.3.3 Oxygen Purifiers—Reagent-grade oxygen from a 25.6.1 It has been found through round robin studies that the
commercial tank is passed through a suitable two-stage reduc- practice of pre-igniting samples at 1000°C causes erratic
tion valve to provide an even and adequate flow of oxygen recovery of sulfur. This practice should not be used.
through a purifying train consisting of a sulfuric acid tower, an 25.7 Procedure:
absorption bulb containing 20 to 30-mesh inert base impreg- 25.7.1 Allow 15 min for the electronics in the furnace
nated with NaOH, and another absorption bulb containing assembly and titrator to warm up.
anhydrous magnesium perchlorate Mg (ClO4). A flowmeter 25.7.2 Set the grid-current tap switch to low, medium, or
precedes the induction furnace assembly. high position. Determine the position on a test run, with the
25.3.4 Combustion Crucibles—The crucibles for use with sample and accelerators that will give a complete combustion
the induction furnace must be of adequate thickness to retain at approximately 400 mA as indicated on the plate current
the molten slag and have a sulfur blank as low and consistent ammeter.
19
C25 − 17
25.7.3 Set the automatic timer to the estimated time re- R
F5 (21)
quired to evolve the sulfur in the sample completely, as ~A 2 B!/~W 3 2!
follows:
where:
Sample Time, Min
Quicklime 8 A = buret reading as % Sulfur (S),
Hydrated Lime 10 B = buret reading for Blank determination,
Limestone 12 R = % Sulfur (by Sodium Carbonate Fusion Method) of the
25.7.4 Weigh the sample and brush carefully into the reference material, and
combustion crucible using the loading funnel. The correct W = weight of sample, g.
sample weight is determined by the estimated sulfur content of 25.8.2 Calculate the percentage of sulfur in the sample by
the sample as follows: using furnace factor F.
Sulfur % Sample Weight (g)
0.001 0.500
A2B
25.7.5 The choice of accelerators is left to the discretion of %S5F3 (22)
W 32
the user, as each furnace will burn differently in accordance
with type and amount used. Generally, the more accelerator where:
used, the greater the furnace temperature. Tin metal, iron chip, A = buret reading as % Sulfur (S),
iron powder, and copper ring have been found to be suitable B = buret reading for Blank determination,
materials. Porous covers should be used to prevent splattering F = furnace factor, and
of the hot flux and damage to the combustion tube. Do not W = weight of sample, g.
re-use crucibles or covers. 25.9 Precision and Bias:
25.7.6 Run a blank determination before each series (of 25.9.1 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. for % sulfur given in 25.9.2 and 25.9.3.
25.7.7 Place the crucible and sample on the pedestal and lift 25.9.2 The repeatability (Practice E691 [r]) was found to be
into position in the combustion tube. 0.0070 % sulfur.
25.9.3 The reproducibility (Practice E691 [R]) was found to
25.7.8 With the oxygen flow at 1 L/min, close stopcock on
be 0.0120 % sulfur.
bottom of titration vessel, and add the HCl to the middle of the
bell-shaped portion of the titration vessel. Always fill to the
same level.
25.7.8.1 Add one measure of starch solution to the titration
vessel. Fill the iodate buret. 26. Phosphorus by Molybdovanadate Method
25.7.9 Turn the double throw switch on the titrator to the 26.1 Scope—This method is suitable for the determination
end-point position (down). Slowly rotate the end-point control of small amounts of phosphorous in lime and limestone
in a clockwise direction until it has added KIO3 in the amount samples. The procedure is based on the fact that phosphorous
to give a solid medium blue color. After the indicator light (for in its ortho form will combine with ammonium molybdovana-
solenoid valve) has stopped blinking, place the switch in the date to yield a yellow color that can be measured spectropho-
neutral position and fill the KIO3 buret again. Turn the switch tometrically. Total phosphate is determined after a strong
to the titrate position. oxidation decomposition with perchloric acid.
25.7.10 Turn on the power of the high-frequency furnace.
The temperature will rise in the crucible as indicated by the 26.2 Summary of Test Method—The sample is decomposed
plate current ammeter on the induction furnace that must with perchloric acid, the solution filtered, SiO2 expelled, and
indicate a reading of at least 400 mA before complete com- the insoluble residue fused with Na2CO3. Ammonium molyb-
bustion of sulfur can take place. dovanadate which is then added reacts with the phosphorous in
solution to form the heteropoly phosphomolybdovanadate
25.7.11 As sulfur dioxide is given off, the unit will begin
complex. The absorbance of the solution is measured with a
titrating automatically. The titration is finished when the
photometer at 430 nm and compared against standards simi-
indicator light stops blinking for a period of time, or the iodate
larly treated.
in the buret stops falling over a period of time.
25.7.12 Inspect the crucible for a proper burn. A rough, 26.3 Special Solutions:
bumpy surface or appearance of non-combustion indicates that 26.3.1 Phosphorous Standard Stock Solution (0.5 mg
the furnace temperature was too low. Sticking of the porous P/mL)—Weigh 1.0983 g of potassium dihyrogen phosphate,
cover to the crucible indicates that the furnace temperature may KH2PO4, into a 250-mL beaker and dampen with about 5 to
have been too hot. Both conditions indicate poor sulfur 10 mL of water. Add 10 mL HNO3 and 25 mL HClO4 (see Note
recovery and may be helped by a slight change in accelerator 31), heat on a hot plate, and evaporate to heavy fumes of
amounts. HClO4. Cover and boil until the solution is colorless or slightly
yellow (10 to 15 min). Cool the solution, transfer to a 500-mL
25.8 Calculation: volumetric flask, dilute to volume, and mix. Store in a
25.8.1 Calculation of Furnace Factor (F) borosilicate or plastic bottle with a screw cap.
20
C25 − 17
26.3.2 Phosphorous Working Standard (0.05 mg P/mL)— measure the absorbance at 430 nm using the blank standard
Dilute 50 mL of stock solution 26.3.1 to 500 mL with distilled solution in the reference cell. Compare against a set of
water. Store in a Pyrex or plastic bottle with screw cap. standards similarly treated.
26.3.3 Ammonium Molybdovanadate Solution: 26.6 Calculation:
26.3.3.1 Dissolve 1.25 g of ammonium metavanadate in 26.6.1 Calculate % P2O5 as follows:
400 mL of 1 + 1 nitric acid in a 1 L volumetric flask.
26.3.3.2 Dissolve 50 g of ammonium molybdate in 400 mL
of distilled water. C 3 D 3 2.2913
% P 2O 5 5 (23)
26.3.3.3 Pour solution from 26.3.4.2 into solution 26.3.4.1, W 3 104
mix, and dilute to volume with distilled water. where:
26.4 Preparation of Standard Curve: C = concentration of P in sample solution, µg/mL deter-
26.4.1 To each of seven individual 50 mL volumetric flasks, mined from calibration curve,
add with a buret 0, 1, 2, 4, 6, 10, and 14 mL of phosphorous D = dilution factor, and
working standard solution corresponding to 0, 0.05, 0.10, 0.20, W = g of sample.
0.30, 0.50, and 0.70 mg of phosphorous, respectively. 26.7 Precision and Bias:
26.4.2 Add 1 mL of perchloric acid and dilute to about 26.7.1 The number of laboratories, materials, and determi-
20 mL with water. Add 10 mL of the molybdovanadate nations in this study does not meet the minimum requirements
solution, swirling the contents of the flask during the addition. for determining precision prescribed in Practice E691:
Dilute to volume with distilled water, mix well, and allow to Test Methods Practice E691
stand for 10 min. The prepared standard solutions will contain C25 Minimum
0 (blank), 1.0, 2.0, 4.0, 6.0, 10.0, and 14.0 micrograms (µg) Laboratories 3 6
Materials 5 4
P/mL. Determinations 4 2
26.4.3 Determine the absorbance of each standard solution
in the spectrophotometer at a wavelength of 430 nm using the 26.7.2 The following precision statements are provisional.
blank standard as the reference solution. Prepare a calibration Within five years, additional data will be obtained and pro-
curve by plotting absorbance versus concentration of phospho- cessed which does meet the requirements of Practice E691.
rous in µg/mL. 26.7.2.1 Precision, characterized by repeatability, Sr and r,
and reproducibility, SR and R, has been determined for the
26.5 Procedure: following test method and materials to be:
26.5.1 Weigh 5.0 g of prepared sample into a 250-mL Precision Statement for
beaker and dampen with about 5 to 10 mL of water. Add 10 mL % P2O5 Color
Test Method:
HNO3 and 25 mL HClO4 (see Note 31), heat on hot plate, and Material Average Sr SR r R
S-1145 0.0031 0.0010 0.0017 0.0029 0.0046
evaporate to heavy fumes of HClO4. Cover and boil until S-1142 0.0091 0.0019 0.0031 0.0053 0.0087
solution is colorless or slightly yellow (10 to 15 min). Cool S-1141 0.0221 0.0014 0.0043 0.0040 0.0122
slightly and add 50 mL H2O. Filter through retentive filter S-1144 0.0657 0.0063 0.0144 0.0175 0.0404
S-1143 0.1353 0.0077 0.0147 0.0215 0.0413
paper and wash thoroughly with hot H2O (see Note 32).
Reserve filtrate.
27. Manganese by the Periodate (Photometric) Method
NOTE 31—If a special perchloric acid hood is not available, the use of
perchloric may be omitted. Instead, add 10 mL HNO3 and evaporate to
27.1 Scope—In this method, periodate is the oxidizing agent
dryness. Take up salts with 5 mL HCl, break up residue, and again used to convert manganous into permanganate ion whose color
evaporate to dryness. Boil up with 1 mL of HNO3 and 20 mL of water, and can then be read in a photometer at a wavelength of 545 nm.
filter, and so forth. This method is capable of determining small amounts of Mn as
NOTE 32—The filter paper and silica residue must be washed free of low as 10 ppm.
perchlorate salts to prevent small explosions from occurring in the
crucible when the filter paper is charred and ignited. 27.2 Summary of Test Method—The same sample solution
26.5.2 Place paper and contents in a platinum crucible and prepared in the determinations of phosphorous by molybdova-
heat gently with a low flame until paper chars. Ignite at a nadate (see 26.5.1 to 26.5.2) can be used for the determination
higher temperature until ash is white. Cool, add 2 drops of of manganese by periodate. The acid solution is oxidized to
H2SO4 (1 + 1) and 10 to 15 mL HF. Evaporate cautiously to permanganate by potassium periodate. Photometric measure-
dryness and heat in a muffle at 1000°C for 2 min (see Note 33). ment is made at 545 nm.
Fuse residue with 0.5 g of Na2CO3, cool, add 5 mL H2O and 27.3 Special Solutions:
1 mL HClO4 and warm to dissolve. Combine the filtrates and 27.3.1 Manganese Standard Solution (1 mL to 50 µg Mn)—
transfer to a 100 mL volumetric flask. Dilute to volume and Dissolve 0.0500 g pure manganese (Mn) metal in 20 mL
mix. H2SO4 (1 + 9) and dilute to 1 L with water.
NOTE 33—The treatment of the residue with HF and H2SO4 may be 27.3.2 Nitric-Phosphoric Acid Mixture—Add 800 mL
omitted if the SiO2 in the sample is low, <3 %. HNO3 and 200 mL H3PO4 to 400 mL of H2O and dilute to 2 L.
26.5.3 Pipet 25 mL of solution into a 50 mL-volumetric 27.4 Preparation of Calibration Curve:
flask and add 10 mL ammonium molydovanadate solution, 27.4.1 Transfer 0, 1, 2, 3, 5 and 10 mL of manganese
dilute to volume and mix well. Allow to stand 30 min and standard solution to six 150 mL beakers, respectively. Add
21
C25 − 17
25 mL of acid mixture to each and heat but do not boil. While 27.7.2 The following precision statements are provisional.
heating, add potassium periodate (KIO3) crystals, a few milli- Within five years, additional data will be obtained and pro-
grams at a time (about 0.3 g total), until the permanganic color cessed which does meet the requirements of Practice E691.
is fully developed. Keep solution near boiling for 10 min after 27.7.2.1 Precision, characterized by repeatability, Sr and r,
color develops; the total heating period should last about 30 and reproducibility, SR and R, has been determined for the
min. following test method and materials to be:
27.4.2 Allow to cool, transfer to a 50-mL volumetric flask, Precision Statement
% Mn Color
dilute to volume and mix. Read absorbance at 545 nm using the for Test Method:
Material Average Sr SR r R
“0” standard (blank) in the reference cell and construct a S-1145 0.0011 0.0004 0.0005 0.0011 0.0014
calibration curve by plotting absorbance versus concentration S-1143 0.0025 0.0005 0.0007 0.0014 0.0020
of Mn in µg/mL. S-1142 0.0147 0.0010 0.0010 0.0028 0.0028
S-1141 0.0271 0.0012 0.0024 0.0034 0.0066
27.5 Procedure: S-1144 0.1096 0.0072 0.0108 0.0200 0.0304
27.5.1 Weigh 2.0 g of prepared sample into a 250-mL
28. Available Lime Index
beaker and dampen with about 5 to 10 mL of water. Add 10 mL
HNO3 and 20 mL HClO4 (see Note 34), heat on hot plate, and 28.1 Scope—The available lime index of high-calcium
evaporate to heavy fumes of HClO4. Cover and boil until quicklime and hydrated lime designates those constituents that
solution is colorless or slightly yellow (10 to 15 min). Cool enter into the reaction under the conditions of this specified test
slightly and add 50 mL H2O. Filter through retentive filter method, otherwise known as the “rapid sugar test method.” The
paper and wash thoroughly with hot H2O (see Note 32). interpretation of results obtained by this test method shall be
Reserve filtrate. restricted by this definition.
NOTE 34—If a special perchloric hood is not available, omit the use of 28.2 Summary of Test Method—The sample is slaked and
HClO4. Instead, evaporate to dryness twice with nitric acid and finally boil dispersed with water. The lime is solubilized by reaction with
with 10 mL HNO3 and 50 mL H2O. sugar to form calcium sucrate which is then determined by
27.5.2 Transfer paper and contents to a platinum crucible titration against standard acid using phenolphthalein as the
and heat until paper chars. Ignite at a higher temperature until indicator.
ash is white. Cool, expel SiO2 with HF and H2SO4, evaporate 28.3 Special Solutions:
to dryness (see Note 33) and fuse residue with Na2CO3. Cool, 28.3.1 Hydrochloric Acid, Standard (1.000 N)—Prepare a
add 10 mL H2O and 2 mL HNO3 and warm to dissolve. solution by diluting 83 mL of HCl to 1 L with CO2-free water.
Combine solution with filtrate reserved in 27.5.1 and transfer to Standardization of sock solution should be performed on a
a 100 mL volumetric flask. Dilute to volume and mix. regular basis at a minimum of once per month. For precision
27.5.3 Transfer an aliquot containing <500 µg Mn to a and bias information on standardization with Na2CO3 or
150 mL beaker. Add 25 mL of acid mixture, heat to near Tris-(Hydroxymethyl) Amino-Methane see Practice E200.
boiling and develop the permanganate color by small additions 28.3.2 Standardization of HCl with Na2CO3:
of KIO3 as directed in 27.4.1. Cool the solution, transfer to a 50 28.3.2.1 Transfer approximately 20 g of primary standard
mL volumetric flask, dilute to volume and mix. anhydrous sodium carbonate (Na2CO3) to a platinum dish or
27.5.4 Record the absorbance at 545 nm using the blank crucible, and dry at 250°C for 4 h. Cool in a desiccator.
standard solution in reference cell as in preparation of standard 28.3.2.2 Weigh accurately 4.4 g to the nearest 0.1 mg of the
curve, and compare against a set of standards similarly treated. dried Na2CO3 and transfer to a 500-mL flask. Add 50 mL of
27.6 Calculation: CO2-free water, swirl to dissolve the carbonate, and add two
27.6.1 Calculate the percent Mn as follows: drops of a 0.1 % solution of methyl red in alcohol. Titrate with
the HCl solution to the first appearance of a red color, and boil
the solution carefully, until the color is discharged (see Note
C 3D
% Mn 5 (24) 31). Cool to room temperature, and continue the titration,
W 3 104
alternating the addition of HCl solution and the boiling and
where: cooling to the first appearance of a faint red color that is not
C = concentration of Mn in sample solution µg/mL deter- discharged on further heating.
mined from calibration curve, 28.3.2.3 Calculation—Calculate normality as follows:
D = dilution factor, and
W = g of sample. A 5 ~ B 3 18.87! /C (25)
27.7 Precision and Bias: where:
27.7.1 The number of laboratories, materials, and determi-
A = normality of the HCl solution,
nations in this study does not meet the minimum requirements
B = Na2CO3 used, g, and
for determining precision prescribed in Practice E691: C = HCl solution consumed, mL.
Test Methods Practice E691 NOTE 35—This titration can also be performed potentiometrically with
C25 Minimum the aid of a glass electrode and a calomel electrode.
Laboratories 4 6
Materials 5 4 28.3.3 Standardization of HCl with TRIS (THAM)—[Tris-
Determinations 4 2 (Hydroxymethyl) Amino-Methane]:
22
C25 − 17
28.3.3.1 Transfer an appropriate amount of primary stan- 28.4.1.3 Add 100 mL of the neutralized sugar solution (or
dard tris-(hydroxymethyl) amino-methane to suitable dish or approximately 40 g of pure cane sugar). Stopper the flask,
crucible and dry in a vacuum at 70°C for 24 h (refer to Practice swirl, and let stand for 15 min to react. (Reaction time should
E200). As an alternative, Tris can also be dried at 105°C not be less than 10 min nor more than 20 min.) Swirl at 5-min
(6 5°C) for 2 h in a regular laboratory drying oven. Cool in a intervals during reaction. Remove stopper, add 4 to 5 drops of
desiccator to room temperature. 4 % phenolphthalein indicator solution and wash down the
28.3.3.2 Preparation of Mixed Indicator—Mix 100 mg of stopper and sides of the flask with CO2-free water.
Bromocresol Green with 2 mL 0.1 N NaOH and dilute with 28.4.1.4 When titrating (see Note 38), first add about 90 %
CO2-free water to 100 mL. Dissolve 100 mg of Alizarin Red S of the acid requirement from a 100-mL buret. Finish the
in 100 mL CO2-free H2O. Mix equal portions of Bromocresol titration, more carefully at approximately one drop per second,
Green and Alizarin Red S solutions to form mixed indicator. to the first disappearance of the pink color, which persists for
28.3.3.3 Weigh approximately 8 g of TRIS to the nearest 0.1 3 s. Note the endpoint and ignore any further return of color.
mg and dissolve in 50 mL of CO2-free water. Add 6 drops of
NOTE 38—A mechanical stirrer may be used during the titration if
mixed indicator (see Note 32) and titrate to a bright yellow desired. Put a clean magnetic stirrer bar into the flask and place the flask
end-point with acid. on the magnetic stirrer. Adjust to stir as rapidly as possible without
incurring any loss by spattering. Unless the operator is familiar with
NOTE 36—This titration can also be performed potentiometrically using previous analyses of the lime under test, and in cases where the available
a suitable pH meter to a pH of 4.70. lime content varies to extremes, it is good practice to run a preliminary test
28.3.3.4 Calculation—Calculate normality as follows: by slow titration to determine the proper amount of acid required to
neutralize the sample.
A 5 B/ ~ 0.121136 3 C ! (26) 28.4.2 Procedure for Hydrated Lime—The procedure for

determining Ca(OH)2 is the same as for CaO with the excep-
where: tion that cold CO2-free water is used and the boiling and
A = normality of the HCl solution, cooling steps are omitted.
B = Tris-(Hydroxymethyl) Amino-Methane used, g,
C = HCl solution consumed, mL. 28.5 Calculation:
28.5.1 Calculate for CaO as follows:
28.3.4 Phenolphthalein Indicator (4 %)—Dissolve 4 g of
dry phenolphthalein in 100 mL of 95 % alcohol.
28.3.5 Sucrose Solution—(40 g of pure cane sugar in solid Available lime ~ CaO! , % 5 N 3 V 3 2.804/W (27)
form may be used per sample in place of a sugar solution. The where:
acidity of each lot of sugar can be determined, and a correction N = normality of acid solution,
applied to the titration.) Prepare a 40 % solution (w/v) using V = standard HCl used (1.000 N), mL,
pure cane sugar and CO2-free water in a large beaker and stir W = weight of sample, g, and
until dissolved. Add several drops of phenolphthalein indicator 2.804 = CaO, g, equivalent to 1 mL of standard acid × 100,
solution. Add 0.1 N NaOH solution dropwise with stirring until or 1 mL of standard HCl = 1 % CaO if exactly
a faint pink color persists. Stock solution of sugar may be made 2.804 g of sample is used.
for convenience; however, it should not be stored for more than
two days. 28.5.2 Calculate for Ca(OH)2 as follows:
28.4 Procedure:
Available lime @ Ca~ OH! 2 # , % 5 N 3 V 3 3.704/W (28)
28.4.1 Procedure for Quicklime:
28.4.1.1 The sample as received at the laboratory shall be where:
thoroughly mixed and a representative sample with minimum N = normality of acid solution,
weight of 100 g shall be taken and pulverized to pass a No. 50 V = standard HCl (1.000 N), mL,
sieve for analysis. Weigh rapidly 2.804 g of the finely pulver- W = weight of sample, g, and
ized sample, brush carefully into a 500-mL Erlenmeyer flask ,mdit> 3.704 = Ca(OH)2, g, equivalent to 1 mL of standard
containing about 40 mL of CO2-free water (see Note 37), and acid × 100 or 1 mL of standard
immediately stopper the flask. HCl = 1.32 % Ca(OH)2 when exactly 2.804
NOTE 37—Water should not be added to the sample because, especially
g of sample is used.
with quicklime, there is a tendency for the material to cake and form 28.6 Precision and Bias:
lumps difficult to completely dissolve in the sugar solution later. On the
other hand, if the lime is added to a little water, a better dispersion of the 28.6.1 Twenty-four laboratories cooperated in the testing of
fine particles occurs, leading to a more rapid dissolution of the sample. It three high calcium quicklimes and one high calcium hydrated
is possible that in the case of quicklime, some slaking action occurs to lime thereby obtaining the repeatability (r) and reproducibility
facilitate the dispersion and solution. (R) (Practice E691) data contained in Table 6.
28.4.1.2 Remove the stopper. Place the flask on a hot plate 28.6.2 The user is cautioned that the repeatability and
and immediately add 50 mL of boiling CO2-free water to the reproducibility are considered adequate for the purposes of the
flask. Swirl the flask and boil actively 1 min for complete test method. However, higher levels of MgO and nonreactive
slaking. Remove from the hot plate, stopper the flask loosely, CaO increase the value of the repeatability (within lab) slightly
and place in a cold-water bath to cool to room temperature. and the reproducibility value (between labs) noticeably.
23
C25 − 17
TABLE 6 Precision Data (Results in % Available CaO) dryness, ignite and weigh (see Note 36). If the mass of the
Material Average r R residue exceeds 0.001 g, the determination may have been
Hydrated lime 71.967 0.367 0.963 improperly accomplished. Replicate determinations should
Magnesian quicklime 88.495 0.479 1.784 then be made to verify the validity of the results, or the residue
Shaft kiln quicklime 94.393 0.398 1.405
Rotary kiln quicklime 94.438 0.337 1.092 examined by X-ray diffraction to determine whether refractory
or highly insoluble minerals are present.
NOTE 41—Occasionally the free silica is contaminated by compounds
not decomposed during fusion or dissolved in the subsequent treatments.
28.6.3 Due to the lack of a recognized industry standard, the The residue then is treated with HF and sulfuric and SiO2 expelled.
bias of this test method has not been determined.
29.4 Calculation—Calculate the percent free silica as fol-
29. Free Silica lows:
29.1 Scope—Free silica is usually present in the acid- Free silica, % 5 ~ A 2 B ! /W 3 100 (29)
insoluble residue of lime and limestone samples. This method where:
is applicable to the determination of free silica when it exceeds
A = crucible + insoluble residue, g,
0.05 %. B = crucible minus SiO2, g, and
29.2 Summary of Test Method—After dissolution of a large W = sample, g.
sample of lime or limestone, the insoluble matter including 29.5 Precision and Bias—The precision and bias of this test
SiO2 is separated, ashed, and the oxides fused with pyrosulfate. method have not been determined.
The silicic acid liberated from the clay minerals in the
insoluble matter is dissolved in a hot solution of sodium 30. Unhydrated Oxides Calculated on As-Received Basis
hydroxide but the free silica is unaffected.
30.1 Scope—From the analytical determinations made in
29.3 Procedure:
accordance with the preceding sections, it is possible to
29.3.1 Weigh 5.0 g of the prepared sample in a 400-mL
calculate combined water, CaCO3, and CaSO4 in samples of
beaker, add 25 mL of HCl (1 + 1), and heat to a boil. Using a
lime and hydrated lime. Unhydrated oxides of MgO in hy-
retentive paper, filter the insoluble matter including SiO2 and
drated lime can also be calculated.
wash several times with hot water. Discard the filtrate.
29.3.2 Place the paper containing the insoluble matter in a 30.2 Summary of Test Method—Determine the percent of
platinum crucible and char the paper without inflaming at low free water, LOI, CO2, SO3, CaO, and MgO in accordance with
heat. Increase the heat to burn off the carbon, but do not exceed the preceding sections. Calculate combined H2O, calcium
600 6 50°C. Cool, add approximately 10 g of fused and carbonate, calcium sulfate, and unhydrated magnesium oxide
powdered KHSO4 or K2S2O7 in the platinum crucible, and using the following procedures.
blend thoroughly with a small spatula. Fuse thoroughly over a 30.3 Procedure:
gas burner, first by gradual heating to prevent loss of SO3. 30.3.1 Calculate percentage of combined water in quicklime
When the fusion becomes quietly molten, finish the fusion at a from the loss on ignition and CO2 determinations, as follows:
dull red heat not over 800°C.
Combined H 2 O, % 5 % LOI 2 % ~ CO2 1FM! (30)
NOTE 39—Do not continue heating to a point where salts begin to freeze
on top of the melt and on the sides of the crucible because of the difficulty 30.3.2 Calculate the percentage of combined water in hy-
of subsequent solution. drated lime from the LOI, CO2, and free moisture (FM)
29.3.3 Cool the crucible and its contents and dissolve the determinations as follows:
melt by heating with 150 to 200 mL of water in a 400-mL Combined H 2 O, % 5 % LOI 2 % ~ CO2 1FM! (31)
beaker. To the warm solution, cautiously add approximately
12 g of NaOH pellets a few at a time to dissolve the 30.3.3 Calculate the percent unhydrated oxides on the
precipitated silicic acid (see Note 39). Digest on a hot plate for as-received basis as follows (see Notes 42-44):
30 min at 80 to 90°C. NOTE 42—The calculations involved in determining the percentage of
unhydrated oxides on the as-received basis are illustrated in Table 7.
NOTE 40—Free silica is not transformed to silicic acid by the fusion and NOTE 43—This method for calculating the percentage of hydrated
is not affected by the caustic treatment. oxides is intended primarily for use with Type S hydrated lime.
29.3.4 Filter quickly, using a retentive paper; thoroughly NOTE 44—It is recognized that the results from this method of
scrub and wash the beaker with hot water. Wash the filter paper calculation may not be in strict accord with the actual composition of the
material. Experience indicates, however, that these results provide an
and its contents ten times with hot water; five times with hot index to the performance of the material in practice. The value obtained by
dilute HCl (1 + 1) to dissolve iron and other contaminants of this calculation shall be reported to the nearest 0.5 %.
the free silica, and finally five times with hot water or until free
30.3.3.1 Calculate the CaO equivalents of the CO2 and SO3
of acid. Transfer the paper and residue to a tared platinum
as follows:
crucible, ignite at 1000°C to constant weight, cool in a
dessicator, and weigh as free silica. CO2 3 1.275 5 equivalent CaO~ A ! as CaCO3 (32)
29.3.5 To the ignited and weighed residue add 2 drops of SO3 3 0.700 5 equivalent CaO~ B ! as CaSO4 (33)
H2SO4 (1 + 1) and approximately 10 mL of HF, evaporate to
24
C25 − 17
TABLE 7 Example of Calculation, Unhydrated Oxides
Values Determined From Residual
Compound Factors Calculated Values, %
Chemical Analysis, % Values
CO2 0.40 × 1.275 = equivalent CaO = 0.51
SO3 0.48 × 0.700 = equivalent CaO = 0.34
CaO 42.79 – (0.51 + 0.34 = 0.85) = 41.94 × 0.3213 = equivalent H2O = 13.48
H2O 25.09 – 13.48 = 11.61 × 2.238 = equivalent MgO = 25.98
MgO 30.68 – 25.98 = unhydrated MgO = 4.70
30.3.3.2 Subtract the sum of these CaO equivalents from the solution buffered to pH 10 with NH3 · NH4Cl using Calmagite
total CaO: as the indicator. MgO is calculated by subtracting the EDTA
Total CaO 2 ~ A1B ! 5 hydrated CaO~ C ! (34) equivalent to CaO present from the EDTA equivalent to
CaO + MgO.
30.3.3.3 Calculate the H2O equivalent of the remaining CaO
as follows: 31.3 Reagents:
31.3.1 EDTA Solution (0.4 %)—Dissolve 4 g of disodium
dihydrogen ethylenediamine tetraacetic acid in water and dilute
Hydrated CaO~ C ! 3 0.3213 5 equivalent H2 O ~ D ! as Ca~ OH! 2 to 1 L.
(35) 31.3.2 Potassium Hydroxide, Standard Solution (1 N)—
30.3.3.4 Subtract this value for H2O (D) from the combined Dissolve 56 g of KOH in 1 L of distilled water.
water as calculated in 30.3.1 and 30.3.2. 31.3.3 Ammonia Buffer (pH 10.5)—Dissolve 67.5 g of
NH4Cl in 300 mL of distilled water, add 570 mL of NH4OH,
Combined water 2 H 2 O ~ D ! 5 equivalent H2 O ~ E ! as Mg~ OH! 2
and dilute to 1 L.
(36) 31.3.4 Hydroxy Naphthol Blue (calcium indicator)—
30.3.3.5 Calculate the MgO equivalent of the remaining Disodium salt of 1-(2-naphthol azo-3,6 disulfonic acid)2
water (E) as follows: naphthol-4-sulfonic acid on suitable carrier.
31.3.5 Calmagite (magnesium + calcium indicator)—1-
H 2 O ~ E ! 3 2.238 5 equivalent MgO ~ F ! as Mg~ OH! 2 (37)
(hydroxyl-4-methyl-2 phenylazo)-2 naphthol-4 sulfonic acid
30.3.3.6 Subtract this MgO equivalent (F) from the total on a suitable carrier.
MgO as determined from preceding sections to obtain the
NOTE 45—Both the hydroxy naphthol blue and Calmagite indicators are
percentage of unhydrated MgO on the as-received basis. manufactured by Mallinckrodt Chemical Works, St. Louis, MO. Each
indicator is a diluted mixture of dye plus an inert carrier.
Total MgO 2 MgO equivalent ~ F ! 5 unhydrated MgO (38) 31.3.6 Hydrochloric Acid (1 + 1).
31.3.7 Hydrochloric Acid (1 + 9).
31. Calcium and Magnesium Oxide (Alternative EDTA
31.3.8 Triethanolamine (1 + 2).
Titration Method)
31.3.9 Potassium Cyanide Solution (20 g/L)—Dissolve 2 g
31.1 Scope—This test method is a rapid EDTA complexo- of KCN in 100 mL of water.
metric method for determining calcium and magnesium in lime 31.3.10 Calcium Standard Solution (1.00 mg CaO/mL)—
and limestone products. Ordinarily the EDTA procedure is Weigh 1.785 g of CaCO3, primary standard grade. Dissolve in
designed to follow routine separations, that is, single dehydra- HCl (1 + 9) and dilute to 1 L with distilled water.
tion of silica and a single precipitation with NH4OH of the 31.3.11 Magnesium Standard Solution (1.00 mg MgO/
combined oxides of iron and aluminum. For expediency, the mL)—Dissolve 0.603 g of magnesium metal turnings in HCl
assays can be run directly without prior separation of the and dilute to 1 L with distilled water.
combined oxides of iron and aluminum by using the complex-
ing action of EDTA at appropriate pH levels. 31.4 Apparatus:
31.4.1 Magnetic Stirrer with light.
31.2 Summary of Test Method: 31.4.2 Stirring Bar, TFE-fluorocarbon-covered.
31.2.1 In this test method, calcium and magnesium are
determined by EDTA titration after separation of silica and the 31.5 Standardization:
NH4OH group during a routine analysis of lime and limestone. 31.5.1 Calcium—Pipet 10 mL of standard CaO solution into
The assays may also be made after a direct HCl decomposition an Erlenmeyer flask and add 100 mL of distilled water. To
followed by removal of the silica and insoluble. prevent precipitation of calcium, add about 10 mL of EDTA
31.2.2 If interfering elements are present in large enough titrating solution. Adjust to pH 12 to 12.5 with about 15 mL of
quantities to cause problems, the interferences may be sup- 1 N KOH solution and stir. Add 0.2 to 0.3 g of hydroxy
pressed by the addition of complexing or masking agents such naphthol blue indicator (see Note 46) and complete titration to
as triethanolamine or cyanide. a clear blue end point (see Note 47). Titrate three or more
31.2.3 For the determination of calcium, the solution is aliquots and use the average to calculate the titer of the CaO
adjusted to a pH of 12 to 12.5 with KOH solution and titrated solution.
with EDTA to a blue end point using hydroxy naphthol blue as CaO titer, mg/mL 5 10 mg CaO standard⁄mL EDTA titration (39)
the indicator. Both CaO and MgO are then titrated from a NOTE 46—The amount of indicator is usually a matter of individual
25
C25 − 17
preference, but if Mallinckrodt reagents are used, the recommended TABLE 9 Precision of Magnesium Oxide
dosages are considered the proper amounts to add for easy end point Repeatability Reproducibility
detection. Sample MgO Within Between
NOTE 47—The use of a magnetic stirrer with light may be very helpful Tested Found Laboratories Laboratories
in detecting the color change. The end point is the first definite blue color A-1a 1.58 0.19 0.18
that remains stable for at least 30 s. A-2b 21.58 0.24 0.41
L-1 0.58 0.21 0.22
31.5.2 Magnesium—Pipet 10 mL of the 1.00-mg/mL stan- P-1a 1.45 0.23 0.24
dard MgO solution into an Erlenmeyer flask and add 100 mL Pooled ... 0.22 0.28
of distilled water. Adjust to pH 10 with 10 mL of the
ammonium chloride-ammonium hydroxide buffer solution, and
add 0.3 to 0.4 g of Calmagite indicator (see Note 46). Titrate
with disodium EDTA, noting the color change from a red to basic and prescribed disposal procedures used. Waste cyanide
deep blue end point (see Note 47). Titrate three or more solutions must not be poured down laboratory sinks. Such
aliquots and use the average to calculate the magnesium titer. solutions can be rendered relatively harmless by making them
MgO titer, mg/mL 5 10 mg MgO standard⁄mL EDTA titration (40)
strongly basic, pH 12 or higher, with sodium hydroxide, adding
calcium hypochlorite, and letting the solution stand for 24 h.
31.6 Procedure: 31.6.4.3 Add 0.2 to 0.3 g of hydroxy naphthol blue indicator
31.6.1 If using limestone, dry the sample at 110°C to (see Note 41) and titrate as in 36.5.1 to a clear blue end point
constant weight and cool to room temperature. (see Note 47).
31.6.2 Weigh 0.5 g of the dry sample into a 250-mL beaker, 31.6.4.4 Calculation:
add 10 mL of HCl (1 + 1), and carefully evaporate to dryness
CaO, % 5 CaO titer 3 mL EDTA 3 1.25/weight of sample, g (41)
on hot plate. Dissolve residue in 25 mL of HCl (1 + 9), dilute
to about 100 mL with water, and digest at low heat for 15 min. 31.6.5 Magnesium Oxide:
Cool, transfer to a 250-mL volumetric flask, dilute to volume, 31.6.5.1 Pipet a 20-mL aliquot of the acid solution from the
mix, and let settle or filter using a medium textured paper. 250-mL volumetric flask and transfer to an Erlenmeyer flask.
31.6.3 Alternatively, if the standard procedure has been Dilute with 100 mL of water, add about 20 mL of ammonia
used to determine the silica and insoluble and iron and buffer to pH 10, and stir.
aluminum, the filtrate remaining after the precipitation of the 31.6.5.2 Add 2 to 3 drops of 2 % potassium cyanide
iron and aluminum with ammonia can be used for the Ca and solution, or 10 mL of triethanolamine and 1 drop of trietha-
Mg EDTA determination. Continue the analysis as follows: nolamine (Warning—See 31.6.4.2) (see Note 49). Add EDTA
Acidify the filtrate with HCl, transfer to a 250-mL volumetric standard solution equivalent to calcium titration; then add
flask, dilute to volume with distilled water, and mix. approximately 0.4 g of Calmagite indicator (see Note 41).
31.6.4 Calcium Oxide: 31.6.5.3 Titrate to a blue end point with the 0.4 % EDTA
31.6.4.1 Pipet a 20-mL aliquot from the 250-mL volumetric solution (see Note 47).
flask and transfer to an Erlenmeyer flask. Dilute to 150 mL 31.6.5.4 The titration determines both the calcium and
with water, adjust the pH to 12 with about 30 mL of 1 N KOH magnesium present in solution. Subtraction of the EDTA
solution, and stir. titration obtained for calcium from the total titration gives the
NOTE 48—Precipitation of calcium hydroxide can be prevented, if titration value for magnesium.
necessary, by adding one half to one third of the estimated volume of 31.6.5.5 Calculation:
disodium EDTA solution before the addition of the potassium hydroxide. mL EDTA solution equivalent to MgO
Presence of a large precipitate can cause loss of sharpness in the end point.
5 ~ mL EDTA solution used in CaO + MgO titration!
31.6.4.2 If the sample is known to contain significant
quantities (>1 %) of iron, manganese, and heavy metals (see 2 ~ mL EDTA solution used in CaO titration! (42)
Note 49), add 2 to 3 drops of 2 % potassium cyanide solution,
or 10 mL of triethanolamine.
MgO, % 5 mL EDTA equivalent to MgO 3 MgO EDTA titer
NOTE 49—If silica and phosphate or excessive amounts (>5 %) of iron
3 1.25⁄weight of sample, g (43)
and aluminum are present, they should first be removed by a double
ammonia precipitation as in the standard procedure. 31.7 Precision and Bias:9
Warning—Cyanides should be used with utmost care be- 31.7.1 The precision of this test method was tested by ten
cause they can be very toxic compounds. They should be kept laboratories using three limestone and one dolomite reference
samples. The results shown in Tables 8 and 9 are summarized
as follows:
TABLE 8 Precision of Calcium Oxide 31.7.1.1 The overall precision (1 sigma) between laborato-
Sample CaO Repeatability 1 Reproducibility 1 ries (reproducibility) for CaO is 6 0.31 absolute units.
Tested Found sigma sigma 31.7.1.2 The overall precision (1 sigma) between laborato-
A-1a 53.48 0.31 0.27 ries for MgO is 6 0.28 absolute units.
A-2b 30.98 0.28 0.41
L-1 53.92 0.29 0.26
P-1a 53.88 0.31 0.28
9
Pooled ... 0.30 0.31 Supporting data have been filed at ASTM International Headquarters and may
be obtained by requesting Research Report RR:C07-1000.
26
C25 − 17
31.7.1.3 The overall precision (1 sigma) within laboratories neity. Tests made on NIST steel standards have shown that they are
(repeatability) for CaO is 6 0.24 absolute units. sufficiently homogeneous to permit the use of samples as small as 20 mg.
31.7.1.4 The overall precision (1 sigma) within laboratories 32.6.2 Condition the analyzer if more than 2 h have elapsed
for MgO is 6 0.22 absolute units. since the last sample was run and determine the blank reading
as follows:
32. Total Carbon by Direct Combustion-Thermal
Conductivity Cell Method 32.6.2.1 Load into a crucible 1.5 g of iron chip accelerator
and 1 g of tin-coated copper.
32.1 This test method covers the determination of carbon in
32.6.2.2 Proceed as directed in 32.7.1 to 32.7.4.
lime and hydrated lime samples having a carbon concentration
in the range from 0.005 to 5 %. 32.6.2.3 Repeat 32.6.2.1 and 32.6.2.2 a sufficient number of
times to establish that low and consistent blank readings are
32.2 Summary of Test Method—All the carbon in the sample obtained.
is converted to CO2 by combustion in a stream of purified
oxygen using an induction furnace. Under some conditions, 32.6.2.4 The normal blank reading should be 0.007 to
CO is formed and a catalyst furnace is used to convert it to 0.009. If it is out of this range, determine the cause, correct it,
CO2. The products of combustion are swept into the carbon and repeat the steps as directed in 32.6.2.1 through 32.6.2.2.
analyzer where the CO2 is selectively absorbed by a molecular 32.6.3 Calibration Curve:
sieve. The CO2 is later released and swept by a fresh stream of 32.6.3.1 The calibration of the analyzer should be done
oxygen past a thermal conductivity cell which senses the using carbon standards that bracket the percent carbon in the
amount of CO2 present. The signal from the sensor is amplified samples estimated from previous tests, using the following
and electronically converted to % C which is displayed on a guidelines:
digital readout panel. High-Carbon Low-Carbon
% Carbon in Sample Standard, % Standard, %
32.3 Apparatus: 0.5–1 1.0 0.4
32.3.1 Combustion Furnace and Carbon Determinator— 0.2–0.5 0.6 0.2
This unit is commercially available. 0.1–0.2 0.2 0.1
0.02–0.1 0.1 0.01
32.3.2 Crucibles—Use crucibles recommended by the
manufacturer of the instrument. 32.6.3.2 Treat each standard as directed in 32.7.1 to 32.7.4.
32.3.3 Oxygen Cylinder with Two-Stage Regulator. 32.6.3.3 Select two standards, one slightly higher and the
32.3.4 Purifying Train, consisting of a sulfuric acid tower, other slightly lower than the carbon concentration of the
an absorption bulb containing Ascarite and another absorption sample.
bulb containing Anhydrone. A flowmeter precedes the induc- 32.6.3.4 Run the high standard first and observe the reading.
tion furnace assembly. The carbon reading should be within 6 1 % of the standard
32.3.5 Catalyst Furnace, to convert CO to CO2. carbon value plus the blank (see Note 51). If it is within this
32.3.6 Combustion Tube with Built-In Jet. range, proceed to 32.6.3.7.
32.4 Reagents:
NOTE 51—For example, with a blank reading of 0.009, a carbon
32.4.1 Iron Chip Accelerator, low-carbon. standard which has a standardized value of 0.428 % should read 0.433 to
32.4.2 Copper-Tin Accelerator. 0.441.
32.5 Preparation of Apparatus: 32.6.3.5 If the reading is out of this range, run a duplicate
32.5.1 Assemble the apparatus. Start the flow of oxygen at sample.
1500 mL/min and the carrier gas flow at the rate recommended 32.6.3.6 If the second sample has approximately the same
by the manufacturer of the apparatus. value as the first sample, adjust the slope control (see Note 52)
32.5.2 Test the furnace and the analyzer to ensure the to bring the reading to within the tolerance of the standard.
absence of leaks and make the required electrical power
connections. Prepare the induction furnace and analyzer for NOTE 52—Not all manufacturers may have this particular feature in
calibration and sample analysis according to the manufactur- their instrument, in which case the manual of instructions supplied with
er’s manual of instructions. each instrument should be adhered to very closely and the instructions
followed.
32.5.3 After the instrument has been prepared for
calibration, check the CO2 collection time which should have 32.6.3.7 Run a carbon standard that has a carbon value
an 80 to 90-s time duration. The collection time can be checked lower than the sample as directed in 32.6.3.1 to 32.6.3.3.
by operating without a sample. If it is outside of this range, 32.6.3.8 The reading should be within +1 % of the carbon
make the necessary adjustment of the collect relay as provided value plus the blank (see Note 52).
for in the manual of instructions. 32.6.3.9 If the reading is within tolerance range, proceed to
32.6 Calibration: sample analysis, 32.7.1 to 32.7.4.
32.6.1 Select NIST steel calibration standards containing 32.6.3.10 If the reading is out of the tolerance range, run a
approximately 0.02 to 1 % carbon (see Note 50). duplicate sample. If the second sample has the same out of
NOTE 50—The accuracy of this test method is dependent to a large tolerance value as the first sample, repeat 32.6.3.4 to 32.6.3.9,
extent on the accuracy of the methods used to certify the carbon readjusting the slope control to bring the high standard within
concentration in the calibration standards as well as upon their homoge- the tolerance of the standard.
27
C25 − 17
32.6.3.11 If the standards are still out of line, refer to the CO2-free water to 100 mL. Dissolve 100 mg of Alizarin Red S
manufacturer’s manual for instruction, determine the cause, in 100 mL CO2-free H2O. Mix equal portions of Bromocresol
correct it, and repeat the standardization procedure, 32.6.3.2 to Green and Alizarin Red S solutions to form mixed indicator.
32.6.3.8. 33.4.2 Hydrochloric Acid, Standard (1.0 N)—Prepare a
32.7 Procedure: 1.0 N solution of hydrochloric acid (HCl) and standardize.
32.7.1 Stabilize the furnace and analyzer as directed in Refer to available lime index test method for procedure on
32.5.1 to 32.5.3. standardization of hydrochloric acid. For further information
32.7.2 Weigh duplicate samples to the nearest 1 mg, using on preparation and standardization of solutions see Practice
the following guidelines: E200.
33.4.3 Phenolphthalein Indicator Solution (1 g/100 mL)—
Carbon Content, % Sample Weight, g
0 to 0.1 1.000 Dissolve 1.0 g phenolphthalein in 100 mL of alcohol.
0.1 to 2 0.500 33.4.4 Sodium Hydroxide Standard Solution (0.5V AN)—
2 to 5 0.250 Dissolve 20 g of sodium hydroxide (NaOH) in 150 mL of
32.7.3 Transfer the sample to a combustion crucible, add carbon dioxide—free water. Cool the solution to 25°C and
1.5 g of iron chip accelerator and 1 g of the tin-coated copper dilute to 1 L. Prepare free from carbonates and store in a
accelerator. Place the crucible on the furnace pedestal, raise the polyethylene bottle provided with a siphon tube and with guard
pedestal into position, and lock the system. Start the flow of tubes containing soda-lime, or other suitable device, to prevent
oxygen at 1500 mL/min, and flush the system for 30 s. absorption of carbon dioxide (CO2) from the air:
32.7.4 Start the cycle timer which energizes the furnace and 33.4.4.1 Standardize against 1.0 N hydrochloric acid with
starts the programmer, after having set it to provide a combus- three 50 mL aliquots using phenolphthalein solution as indica-
tion cycle of 1 min. Using the variable transformer, manually tor. Take the average of the three results as the normality of the
control the plate current within the range from 350 to 450 mA. Sodium Hydroxide Standard Solution.
When the cycle is complete, remove and discard the crucible.
Record the reading.
V 2N 2
32.8 Calculation—Subtract the value found for the blank in Normality ~ NaOH! 5 (45)
V1
32.6.2.3 from the reading found in 32.7.4 and record the net
reading. Calculate the percentage of carbon as follows: where:
V1 = volume of NaOH Standard Solution,
V 2 = volume of HCl used to neutralize NaOH, and
Carbon, % 5 A/B (44) N2 = normality of HCl Standard Solution.
where: 33.5 Preparation of Sample:
A = net carbon content, %, and 33.5.1 Weigh and dry the limestone and slag samples to
B = sample mass, g. constant weight at a temperature of 110 6 5°C. Record the
32.9 Precision and Bias—The precision and bias of this test as-received and dry weights in order to calculate moisture
method have not yet been determined. content. Use lime samples as received. Grind the sample to
pass a No. 60 (250-µm) sieve, mix thoroughly, and store in
33. Calcium Carbonate Equivalent airtight containers.
33.1 Scope—The calcium carbonate equivalence (CCE) test 33.6 Procedure:
is used to determine the neutralizing capability of a calcareous 33.6.1 Indicator Titration Method—Using Table 10 as a
material and to report this value in terms of percent calcium guide (see Note 53), weigh the material, to the nearest 0.1 mg,
carbonate equivalents (% CaCO3). and place into a 500-mL Erlenmeyer flask; add 100 mL of
33.2 Significance and Use—Calcareous materials such as 1.0 N HCl and boil gently for 5 min. Cool, and titrate the
crushed limestone, hydrated lime and pulverized slags (from excess acid with 0.5 N NaOH solution using phenolphthalein
the production of steel) have been used extensively as soil as indicator. Calculate CCE as described in 33.6.3.
modifiers or agricultural liming materials. A measure of their 33.6.2 Potentiometric Titration Method (applicable to agri-
neutralizing capability can be determined through the use of cultural liming materials containing large amounts of ferrous
this method of test. Not all neutralizing components of acal- iron or coloring matter, but not to silicate materials)—Proceed
careous material may be beneficial, therefore, the chemical as in 33.6.1 through “Cool. . .”. Transfer to a 400-mL beaker
analysis is suggested. and insert glass and calomel electrodes of a pH meter and a
mechanical stirrer. Stir at a moderate speed to avoid splash.
33.3 Apparatus: Deliver from a buret the 0.5 N NaOH solution rapidly to pH 5,
33.3.1 pH Meter, conforming to Sections 4 and 5 of Test then dropwise until the solution attains pH 7 and remains
Method E70. constant for 1 min while stirring. Report as CaCO3 equivalent
33.3.2 Mechanical Stirrer. as described in 33.6.3.
33.3.3 Sieve, No. 60 (250-µm). 33.6.3 Calculation of Percent Calcium Carbonate Equiva-
33.4 Reagents: lence:
33.4.1 Preparation of Mixed Indicator—Mix 100 mg of 33.6.3.1 Dry Basis:
Bromocresol Green with 2 mL of 0.1 N NaOH and dilute with
28
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TABLE 10 Recommended Sample WeightA
Sample Type Formula Purity, % Theoretical C.C.E. Sample Weight, g
Magnesium oxide MgO 97 248.33 1.9
Dolomitic lime CaO MgO 97 207.69 2.3
Calcium oxide CaO 97 178.48 2.6
Dolomitic Type N hydrate Ca(OH)2 MgO 98 175.01 2.6
Dolomitic Type S hydrate Ca(OH)2 Mg(OH)2 98 151.21 3.0
Calcium hydroxide Ca(OH)2 98 135.11 3.4
Dolomitic limestone CaCO3 MgCO3 97 108.56 4.3
Calcium carbonate CaCO3 97 100.00 4.6
A
For those materials not listed in Table 10: To determine the amount of 1.0 N HCl required for neutralization, a preliminary titration using 2 g of sample (weighed to the
nearest 0.1 mg) should be performed to a yellow end point using mixed indicator. Using the following formula, determine the sample weight need for testing and proceed
to 33.6.1.
Wu p 100
Wr, grams s g d 5
Vu110
where:
Wr = sample weight required for testing, g,
Wu = sample weight used in preliminary titration, g, and
Vu = volume of 1.0N HCl used in preliminary titration, mL.
5.0045 ~ V 1 N 1 2 V 2 N 2 ! 34.4 Special Solutions:

% CaCO3 ~ dry! 5 (46)
W 34.4.1 Potassium Chloride Solution (0.2 M)—Dry reagent
grade KCl crystals at 110°C for 1 h. Dissolve 14.91 g of the dry
where:
KCl in CO2-free deionized water and dilute to 1 L.
V1 = HCl solution used, mL, 34.4.2 Sodium Hydroxide Solution (0.2 M)—Dissolve 8.00 g
N1 = normality of HCl solution, of NaOH in CO2-free deionized water and dilute to 1 L.
V2 = NaOH solution required for titration of excess acid,
Standardize this solution with potassium acid phthalate using
mL,
phenolphthalein as the indicator.
N2 = normality of NaOH solution, and
W = sample weight, g. 34.4.3 Hydroxide-Chloride Buffer Solution (pH 13.0 at
25.0°C)—Dilute 25.0 mL of the KCl solution and 66.0 mL of
33.6.3.2 As-received basis (limestone only): the NaOH solution to 100 mL with CO2-free deionized water.
34.4.4 Phenolphthalein Indicator—Dissolve 4 g of dry phe-
% CaCO3 ~ as received! 5 @ 1 2 ~ A 2 B/A ! # 3 % CaCO3 ~ dry! (47) nolphthalein in 100 mL of 95 % alcohol.
34.4.5 Commercially available pH buffer solutions, pH 7
where: and pH 10.
A = as received sample weight from 33.5.1, and
34.5 Standardization of Sodium Hydroxide Solution:
B = dry sample weight from 33.5.1.
34.5.1 Initial Standardization—Transfer 50.0 mL of the
34. pH of Alkaline Earth Solutions sodium hydroxide solution to be standardized to a well rinsed
50-mL Class A buret by means of a pipette. Accurately weigh
34.1 Scope—This method covers the electrometric pH
out 8.0 6 0.1 g of reagent grade potassium hydrogen phthalate
analysis of solutions made from a variety of lime, hydrate, and
which has been dried in an oven at 110°C for 1 h. Record the
limestone-bearing materials.
weight to the nearest 0.1 mg, then quantitatively transfer the
34.2 Summary of Test Method—In this test method a sample weighed material into a 400-mL beaker. Add 185 mL of
of material is mixed with CO2-free deionized water so that the CO2-free deionized water which is at a temperature of
pH of the solution is determined electrometrically. To ensure 26.0 6 2.0°C. Stir this mixture gently until all of the crystals
that an accurate measurement of pH is obtained for samples dissolve. Add five drops of the phenolphthalein indicator
with a pH greater than 11.5, it is critical that all samples and solution and proceed to titrate the prepared standard with the
buffer solutions be at 25.0°C when measured. sodium hydroxide solution to be standardized. Titrate to an
34.3 Special Apparatus: endpoint of light pink which will persist for at least 6 s.
34.3.1 pH Meter—A commercially available pH meter ca- 34.5.2 Calculation of Sodium Hydroxide Normality—The
pable of calibration with a minimum of two different buffers normality of the sodium hydroxide solution can be calculated
(see Note 53). from the following equation:
NOTE 53—It is necessary that the pH meter be equipped with a Wt. of potassium hydrogen phthalate
Normality of NaOH 5 (48)
combination pH electrode as well as a temperature compensation probe. It mL of NaOH 3 factor of 0.204228
is strongly recommended that a combination pH and temperature com- This preliminary standardization may reveal the necessity for
pensation probe be used. either dilution with CO2-free deionized water or the 0.2 mo-
34.3.2 Constant Temperature Water Bath—The water bath larity specified.
should be large enough to hold all samples and buffer solutions 34.5.3 Correction if Base is “too weak”—If the molarity
necessary to perform this method. (normality) is determined to be too weak, it can be adjusted by
29
C25 − 17
the addition of additional sodium hydroxide. An example of 200 mL of CO2-free deionized water. Add a magnetic stir bar,
this calculation follows. If 1.0 L of 0.1979 N solution needs to immediately stopper the flask with a rubber stopper, and stir for
be strengthened to 0.2000 N, calculate how many grams of 30 min.
sodium hydroxide need to be added as follows: 34.7.2 Let the solution stand for at least 30 min to allow the
suspended material to settle out from the suspension, as well as
1.0 L 3 0.1979 M 5 0.1979 mole (49) to allow the sample temperature to stabilize at 25.0 6 3.0°C. A
constant temperature water bath may be necessary to obtain the
0.2 M 2 0.1979 M 5 0.0021 M desired temperature range.
34.7.3 Once the temperature of the sample is stabilized at
NaOH 5 39.997 g/mole 25.0 6 3.0°C, using a 50-mL transfer pipette, transfer 50 mL of
the settle solution to a 100-mL beaker containing a magnetic
39.997 g/mole 3 0.0021 mole 5 0.0830 g needed
After the addition of additional sodium hydroxide is stir bar.
completed, recheck the standardization as specified in section 34.7.4 Slowly stir the sample solution using a magnetic
34.4. stirrer. Using a previously standardized pH meter, standardized
in accordance with section 34.6, quickly measure the pH of the
34.5.4 Correction if Base is “too strong”—If the molarity
sample. Report the pH to four significant figures.
(normality) is determined to be too strong, it can be adjusted by
the addition of CO2-free deionized water. An example of this 34.8 Procedure—Materials With pH of 11.5 and Greater:
calculation follows. If 1.0 L of 0.2019 N solution needs to be 34.8.1 Weigh 10.0 g of the prepared sample and record the
weakened to 0.2000 N, calculate how many millilitres of weight to the nearest 0.1 mg. 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. Add a magnetic stir bar,
immediately stopper the flask with a rubber stopper, and stir for
1.0 L 3 0.2019 M 5 0.2019 mole
30 min.
0.2019 2 0.200 5 0.0019 L or 1.9 mL of CO2 2 (50) 34.8.2 Place the sample solution into a constant temperature
free deionized water needed water bath set at 25.0°C. Let the solution stand for at least 30
After the addition of additional CO2-free deionized water is min to allow the suspended material to settle out from the
completed, recheck the standardization as specified in section suspension as well as to allow the sample temperature to
34.5. stabilize at 25.0 6 0.1°C.
34.6 Calibration of pH Meter—Due to the wide variety of 34.8.3 Once the temperature of the sample is stabilized at
commercially available pH equipment, a detailed calibration 25.0 6 0.1°C, using a 50-mL transfer pipette, transfer 50 mL of
procedure cannot be incorporated into this test method. Follow the settled solution to a 100-mL beaker containing a magnetic
the manufacturer’s instructions for calibration of your particu- stir bar.
lar equipment. 34.8.4 Slowly stir the sample solution using a magnetic
34.6.1 Using the appropriate combination of the commer- stirrer. Using a previously standardized pH meter, standardized
cially available pH 7 and pH 10.0 buffers, and the Hydroxide- in accordance with section 34.6, quickly measure the pH of the
Chloride buffer (pH 13.0), choose the pair of buffers which best sample solution (see Note 55). It is imperative that the
brackets the pH of the sample being tested. Standardize your temperature of the test solution remain at 25.0 6 0.1°C during
pH meter in accordance with the manufacturer’s instructions. the pH measurement. If needed, the pH measurement should be
For samples with pH less than 11.5, the temperature of the carried out in a constant temperature water bath. Report the pH
samples and buffers should be kept at 25.0 6 3.0°C (see Note to four significant figures.
55). 34.9 Precision and Bias:
NOTE 54—For alkaline solutions in this pH range the temperature does 34.9.1 The number of laboratories, materials, and determi-
not cause errors to the extent that it does with samples with a pH in excess nations in this study does meet the minimum requirements for
of 11.5, therefore the temperature is not as critical. determinating precision prescribed in Practice E691:
For samples with a pH greater than 11.5, it is imperative that Test Methods Practice E691
all solutions be at 25.0 6 0.1°C while they are being measured. C25 Minimum
If all buffers and test solutions are not within this range, due to Laboratories 7 6
Materials 12 4
the high pH being measured, large errors in the measured pH Determinations: 3 2
will occur. This can easily be accomplished by the use of a
34.9.2 Precision Statement for Test Method: pH—Precision,
constant temperature water bath (see Note 56).
characterized by repeatability, Sr and r, and reproducibility, SR
NOTE 55—In strongly alkaline solutions, especially above pH 12, the and R, has been determined for the following materials to be:
concentration of hydroxide ions is so high that the small amount of
Materials Average Sr SR r R
hydrogen ions produced by the ionization of water is sufficient to change
Sample A kiln dust 12.3817 0.0069 0.2791 0.0194 0.7814
the pH appreciably with temperature. Sample B waste lime 12.2998 0.0297 0.4004 0.0831 1.1210
34.7 Procedure—Materials With pH Less Than 11.5: Sample C dolo 12.4073 0.0123 0.2408 0.0345 0.6741
hydrate
34.7.1 Weigh 10.0 g of the prepared sample and record the Sample D dolo lime 12.3942 0.0177 0.2785 0.0495 0.7799
weight to the nearest 0.1 mg. Quantitatively transfer the Sample E −325 stone 11.2199 0.0274 0.3355 0.0766 0.9393
weighed material into a 250-mL Erlenmeyer flask containing Sample F cyclone dust 12.4090 0.0164 0.2336 0.0459 0.6541
30
C25 − 17
Sample G bottom ash 12.1948 0.0120 0.4049 0.0336 1.1338 35.3.1.2 Resistance—The resistance furnace is an open-
Sample H fly ash 9.6776 0.0557 0.3821 0.1559 1.0699 ended combustion system that provides an oxygen environ-
Sample I fly ash 11.3193 0.0143 0.2191 0.0402 0.6136
Sample J hydrate 12.4111 0.0244 0.2994 0.0684 0.8384
ment in two separate areas. A purge flow of oxygen around the
Sample K h. hyd. lime 12.5477 0.0069 0.1875 0.0193 0.5249 front of the combustion area provides an oxygen blanket to
Sample L quicklime 12.4331 0.0260 0.1767 0.0728 0.4949 keep the atmosphere out while acting as a primary source for
combustion. The second oxygen flow is delayed to start after
35. Total Carbon and Sulfur by Combustion/Infrared the majority of the sample has been combusted and provides a
Detection Method direct lance flow of oxygen onto the sample to combust the
35.1 Scope: remaining sample material.
35.1.1 This test method is for the determination of carbon or 35.3.2 Detector—The detector shall consist of one or more
sulfur, or both, in lime and limestone. This test method has also infrared solid-state absorption detectors for carbon or sulfur, or
been adapted for use with kiln flue dusts. This test method both. The detector may be packaged with the furnace unit as
covers the determination of carbon and sulfur in an acceptable long as interference does not occur during analysis.
concentration range from 0.01 to 13 % carbon and from 0.005 NOTE 56—Halogens can be a source of problems. If they are, or are
to 3 % sulfur. suspected to be, present, it is suggested that a halogen trap be used.
35.1.2 Hydrated lime, hydroxides, and samples with high 35.3.3 Combustion Crucibles—The crucibles must be of
moisture cannot be suitably analyzed for sulfur using an adequate thickness and capacity to retain the molten slag and
induction furnace unit. Significant portions of SO2 will be have a sulfur blank as low and consistent as possible.
trapped in the dust filter which will be moist due to the water Warning—There is an explosion hazard associated with the
released or produced from the combustion. These samples analysis of coal and coke in an induction furnace. Flammable
must be analyzed on a resistance-furnace-type unit. Carbon gasses may collect in the IR cell within the closed system.
results will not be similarly effected. Because of the high These types of materials should be analyzed in a resistance
moisture content in the post-combustion gases, moisture filters furnace. See the manufacturer’s instructions and cautions
must be checked often, and when needed, changed. before analyzing any samples.
35.1.3 This standard does not purport to address all of the Warning—It is extremely dangerous to change the oscilla-
safety concerns, if any, associated with its use. It is the tor tube in the induction furnace electrical cabinet. This should
responsibility of the user of this standard to establish appro- only be done by trained personnel. Serious injury or death can
priate safety, health, and environmental practices and deter- result. See manufacturer’s instructions and cautions before
mine the applicability of regulatory limitations prior to use. attempting to change the oscillator tube.
35.2 Summary of Test Method: 35.4 Reagents—Use reagents recommended by the instru-
35.2.1 A sample of lime, limestone, or kiln flue dust is ment manufacturer or their equivalent.
weighed into a ceramic crucible, accelerators are added, and 35.5 Calibration:
the crucible is placed in the furnace. In a pure oxygen 35.5.1 Calibration Standard—This test method and instru-
environment at the high temperatures generated by the furnace, 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. The combustion gases are swept content.
through a drying tube to remove the combustion moisture and 35.5.2 Check Standard—The instrument calibration must be
then swept toward the analyzer. In the analyzer, the gas stream validated on a regular basis (see 35.6.3.6) using a check
passes through the carbon and sulfur infrared detection cells standard. The check standard is used to determine the shift-to-
where measurement occurs. shift variations in the test method and to verify that the
35.2.2 Both carbon and sulfur are calibrated against a electronics are working properly. The check and calibration
reference material or standard with known carbon and sulfur standard cannot be the same standard. The standards must have
concentrations. This is to compensate for characteristics of a a known carbon or sulfur content, or both, either as determined
given apparatus, and for the blank due to accelerators and by a reference method, such as the Total Gravimetric Sulfur
crucibles. Method (see Section 24), or certified upon purchase traceable
35.3 Apparatus: to a nationally recognized standard.
35.3.1 Furnace: 35.6 Procedure:
35.3.1.1 Induction—The induction furnace works by sup- 35.6.1 Instrumental Setup—Clean and perform routine
plying power to an inductor coil, which interacts with the maintenance on furnace and detector units in accordance with
sample and accelerators in a ceramic crucible. The power can recommended procedures in the manufacturer’s operating
be controlled by the voltage to the coil and the accelerators manual. It is recommended that a minimum of three condition-
used in combusting the sample. Some instruments are supplied ing samples be analyzed before instrument calibration.
with a rheostat used to control the power input to the induction 35.6.2 Calibration Procedure:
coil. This is used to avoid heating some types of samples too 35.6.2.1 Prepare blanks, analyze, reset instrument blank
rapidly during the early stages of combustion. Combustion values, and record results. Check with previous blank values
takes place in an oxygen stream, which carries the combustion and if necessary repeat. Prepare calibration samples, analyze,
products through various dust and moisture traps to a detector. reset instrument values, and record results.
31
C25 − 17
35.6.2.2 It is recommended that a check standard be pre- cleaned, or replaced, at regular intervals.
pared and analyzed on a routine basis (see 35.6.3.6). This is to 35.6.3.4 Inspect the crucible for a proper burn. A rough,
verify that routine samples tested during a specific interval are bumpy surface or appearance of noncombustion indicates that
accurate according to the last instrument calibration. the furnace temperature was too low.
35.6.2.3 Run laboratory samples as specified in 35.6.3. 35.6.3.5 After each analysis, record results and continue. It
35.6.3 Sample Procedure: is recommended that samples be saved until results can be
35.6.3.1 Weigh samples to the nearest 0.1 mg in accordance verified by a check standard.
with the manufacturer’s instructions for a specific instrument. 35.6.3.6 Analyze the check standard after a minimum of
NOTE 57—It has been found through round-robin studies that the every 10 samples to verify instrument performance. If the
practice of pre-igniting samples at 1000°C causes erratic recovery of analysis of the check standard is not within tolerance (see Note
sulfur. This practice should not be used. 59), then find the cause and recalibrate.
35.6.3.2 Place the sample in the instrument and perform the NOTE 59—For purposes of this procedure, tolerance can be defined as
analysis. results which meet the published certified value of the standard within the
35.6.3.3 Analysis time is generally 65 s. This can be published standard deviation of the standard’s certified value. The use of
determined by watching the integration time of materials, and NIST traceable standards or comparable is recommended.
finding out what is a normal time for the type of sample you are 35.7 Precision and Bias—The precision and bias of this test
running. If analysis time for sulfur exceeds the normal ex- method have not yet been determined.
pected time, then changing of the Anhydrone tube is recom-
mended as moisture absorption/desorption of SO2 may be 36. Keywords
occurring. Be cautious about the variability of instruments and 36.1 alternative method; aluminum; available lime index;
materials. It is possible to have bimodal curves that indicate a calcium; carbon; carbon dioxide; chemical analysis; free
late release of sulfur. When in doubt, check the instrument with moisture, lime; free moisture, limestone; free silica; hydrated
a material of known concentration. lime; instrumental analysis; iron; limestone; loss on ignition,
(LOI); magnesium; manganese; methods, classical; methods,
NOTE 58—An anhydrone tube that has collected moisture or particu-
lates may “cake” and cause your analysis time to increase. When operating historical; oxides; oxides, unhydrated; phosphorus; quicklime;
the instrument, you can also expect the analysis time to increase due to reference method; silicon dioxide; Standard Reference Mate-
dust and moisture from combustion of the sample. The tube should be rial (SRM); strontium; sulfur
APPENDIXES
(Nonmandatory Information)
HISTORICAL ASTM METHODS
X1. 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. Because they are presently of limited
use, they have been deleted from the main body of reference test methods. Since some laboratories
may still wish to perform these analyses, they have been placed in these appendixes. The precision and
bias testing has not been performed for these methods. Therefore, users are advised to develop their
own laboratory precision and to check against standard reference materials. Subcommittee C07.05
encourages comments and evaluation of these methods.
X1.1 Scope—This test method permits a more accurate X1.3 Special Solutions:
analysis of the trace amounts of iron that may be present
X1.3.1 Manganese Sulfate Solution (70 g/L)—Dissolve 70
because a larger sample is used.
g of crystalline manganese sulfate (MnSO4) in 500 mL of
water. Add 140 mL H3PO4 and 130 mL H2SO4. Dilute to 1 L.
X1.2 Summary of Test Method—The sample is dissolved in
HCl and the SiO2 is dehydrated and separated from the soluble X1.3.2 Potassium Permanganate, Standard Solution
salts by filtration. The small amount of iron left in the insoluble (0.05 N):
residue is dissolved with sulfuric acid after SiO2 is expelled X1.3.2.1 Dissolve 1.60 g of potassium permanganate
with HF, and the recovered iron is combined with the bulk of (KMnO4) in 1 L of water and boil gently in a flask for 20 to
the iron in the main filtrate. Iron is reduced with SnCl2 and 30 min. Cool, dilute again to 1 L, stopper, and allow to stand
titrated with KMnO4 solution. for several days in the dark. Filter through purified asbestos or
32
C25 − 17
a wad of glass fiber and standardize against the National the salts, filter the insoluble matter including SiO2 using a
Institute of Standards and Technology’s standard sample 40C, medium-textured paper, then wash the paper and contents
sodium oxalate (Na2C2O4), or equivalent in accordance with several times with hot water. Retain the filter paper. Heat the
X1.3.2.2 through X1.3.2.4. solution to boiling, add a few drops of methyl red indicator,
NOTE X1.1—Alternatively, potassium dichromate may be used in place
and precipitate the iron by adding enough NH4OH to change
of potassium permanganate as in the procedure of 13.4. the color of the indicator from red to distinct yellow. Allow the
precipitate to settle slightly, filter, and wash using hot water.
X1.3.2.2 Transfer 0.15 g of the standard sodium oxalate,
Dissolve contents of the paper by placing paper and contents in
dried at 105°C, to a 400-mL beaker. Add 250 mL of diluted
50 mL of hot HCl (1 + 3). Filter into a clean beaker and wash.
H2SO4 (5 + 95), which has been previously boiled for 10 min
Reserve filtrate.
and cooled to 27 6 3°C. Stir until the oxalate has dissolved.
Add 40 to 42 mL of the standard KMnO4 solution at the rate of X1.4.2 Place the paper containing the insoluble matter from
25 to 30 mL/min, while stirring slowly. Let stand until the pink the evaporated HCl solution in a platinum crucible. Char the
color disappears (about 60 s). paper without inflaming, at low heat, increase the heat to ash
NOTE X1.2—If the pink color should persist because of the addition of the paper, and ignite at 1000°C for 15 min. Cool, add 1 mL of
too much KMnO4 solution, discard and begin again, adding a few H2SO4 and 10 to 15 mL of HF, and evaporate to fumes of sulfur
millilitres less of the KMnO4 solution initially. trioxide. Cool, dilute the contents of the crucible with water,
X1.3.2.3 Heat the contents of the beaker to 60°C and and warm to dissolve salts. Transfer the acidified solution to
complete the titration at this temperature by adding KMnO4 the main solution containing the bulk of the iron.
solution until a slight pink color persists for 30 s. Add the last X1.4.3 Heat the solution to near boiling. Reduce the iron by
0.5 to 1 mL dropwise, allowing each drop to become decolor- adding SnCl2 dropwise from a pipet, while swirling the beaker
ized before the next one is added. constantly, until the yellow color of the ferric iron just
X1.3.2.4 One millilitre of standard KMnO4 solution will be disappears (see Note 21). Add 2 or 3 drops of SnCl2 in excess,
approximately equivalent to 0.004 g of ferric oxide (Fe2O3). but no more. Cool the beaker quickly in running water, then
Determine the exact Fe2O3 equivalent of the solution from the add all at once 10 mL of HgCl2 solution. Stir and allow to stand
following: for 3 to 5 min (see Note 22). Transfer with washing to a
600-mL of 1-L beaker containing 300 mL of cold water and
N 5 ~ W/V ! 3 14.925 (X1.1) 25 mL of the MnSO4 solution. Titrate with standard 0.05 N
KMnO4 solution, added very slowly while stirring constantly,
where:
until a permanent pink end point is obtained. A blank should
N = normality of KMnO4 solution, also be determined.
W = sodium oxalate, g,
V = KMnO4 solution used to titrate the sodium oxalate X1.5 Calculation—Calculate the percent iron oxide (Fe2O3)
solution, mL, and to the nearest 0.01 % as follows:
14.925 = sodium oxalate equivalent to 1 mL of 1 N KMnO4
solution, g.
Fe2 O 3 , % 5 ~ A 3 B ! /C 3 100 (X1.2)
Fe 2 O 3 equivalent of KMnO 4 = N × 0.07984, where
0.07984 = g Fe2O3 equivalent to 1 mL of 1 N KMnO4 solution. where:
X1.4 Procedure: A = 0.05 N KMnO4 solution used in titration, mL,
B = Fe2O3 equivalent of KMnO4, and
X1.4.1 Weigh 2 to 5 g (depending upon the amount of iron C = sample weighed, g.
present) of the properly prepared sample into a beaker and add
25 mL of HCl (1 + 1). After the reaction ceases, evaporate the X1.6 Precision and Bias—The precision and bias of this test
solution to dryness. Add 50 mL of HCl (1 + 4), heat to dissolve method have not been determined.
33
C25 − 17
X2. STRONTIUM OXIDE BY THE GRAVIMETRIC SULFATE (ETHER) METHOD
X2.1 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).
determination of calcium. This test method is designed to NOTE X2.1—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. nitrates of calcium and strontium were evaporated.
X2.3.3 To the solution of strontium nitrate, in a small beaker
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. The different solubilities of calcium
volume of the nitrate solution. 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. After filtration, the
a period of 12 h.
strontium nitrate precipitate is dissolved with water and the
strontium precipitated with H2SO4 filtered, ignited, and X2.3.4 Filter the SrSO4 on a small filter paper, and wash
weighed as strontium sulfate (SrSO4). with 50 % alcohol. Ignite at low temperature, cool, moisten
with dilute H2SO4 (1 + 1), evaporate to dryness, again ignite,
X2.3 Procedure: and weigh as strontium sulfate (SrSO4). The sulfate may be
X2.3.1 Transfer the weighed oxides obtained in the gravi- tested spectroscopically for traces of calcium and barium if it
metric determination of calcium oxide (see Section 5.1.4) to a is considered necessary.
small flask of 20-mL capacity and dissolve in HNO3. Evapo- X2.4 Calculation:
rate to dryness and heat at 150 to 160°C. Treat the thoroughly
dried nitrates with as little (rarely over 2 mL) of a mixture of X2.4.1 Calculate the mass of strontium oxide as follows:
equal parts of absolute alcohol and ether as may be needed to
dissolve the calcium salt, hastening solution by occasional, SrO, % 5 ~ A/B ! 3 56.41 (X2.1)
gentle agitation. After standing overnight in the stoppered
where:
flask, collect the insoluble matter on the smallest possible filter
and wash with more of the above mixture of alcohol and ether. A = mass of SrSO4,
B = original mass of sample, g, and
Warning—Ethers tend to form peroxides by air oxidation
56.41 = molecular ratio of SrO to SrSO4 × 100.
on standing which are highly explosive. Peroxide containing
ethers should not be distilled unless the peroxide is first X2.4.2 Deduct the percent SrO from the percent CaO
destroyed by a suitable agent such as sodium sulfate or ferrous determined in Section 17.
sulfate and should not be allowed to stand indefinitely in the X2.5 Precision and Bias—This test method was originally
laboratory. approved for publication before the inclusion of precision and
X2.3.2 Let the filter air dry, then pass a few millilitres of hot bias statements within standards was mandated. The user is
water through the filter to dissolve the strontium nitrate. A few cautioned to verify by the use of reference materials, if
tenths of a milligram of residue may remain, consisting of available, that the precision and bias of this test method are
material other than lime or alkaline earth, whose mass should adequate for the contemplated use.
X3. PHOSPHORUS BY THE TITRIMETRIC METHOD
X3.1 Scope—This is a titrimetric test method for determin- then back-titrated with standard acid in the presence of
ing phosphorus in samples of limestone, quicklime, or lime phenolphthalein indicator.
hydrate. A fairly large sample weight is required because this
X3.3 Special Solutions:
test method is not sensitive enough for an accurate analysis at
the low levels of phosphorus frequently encountered in lime- X3.3.1 Ammonium Molybdate Solution:
stone rock. X3.3.1.1 Solution A—Add 400 mL of nitric acid to 600 mL
of water. Mix and cool.
X3.2 Summary of Test Method—The sample is dissolved in X3.3.1.2 Solution B—Dissolve 118 g of 85 % molybdic
dilute nitric acid, the solution filtered, the residue fused with a acid with 400 mL of water and add 80 mL of NH4OH. Cool.
little sodium carbonate and its nitric acid solution added to the X3.3.1.3 Add Solution B to Solution A slowly with constant
other. An HF-HNO3 treatment is included if the rock contains stirring, let solution stand for 24 h. Filter immediately before
more than 3 % SiO2. Ammonium molybdate is added to the using.
nitric acid solution to precipitate phosphorus as ammonium X3.3.2 Potassium Nitrate Solution (10 g/L)—Dissolve 10 g
phosphomolybdate. 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. Dilute to 1 L.
34
C25 − 17
X3.3.3 Sodium Hydroxide, Standard Solution (0.3 N)— X3.4 Procedure:
Dissolve 12 g of sodium hydroxide (NaOH) in 1 L of water that
X3.4.1 Dissolve 10 g of the prepared sample by adding
has been freshly boiled to expel CO2, and cooled. Add 10 mL
80 mL of dilute HNO3 (1 + 1) and heating on hot plate. Add
of a freshly filtered, saturated solution of barium hydroxide
350 mg of ferric nitrate salt (Fe(NO3)3 · 9 H2O) (see Note
Ba(OH)2 (see Note X3.1). Shake the solution frequently for
X3.3) and 15 g of ammonium chloride (NH4Cl), make
several hours and filter it. Store in a stoppered flask protected
ammoniacal, then add 5 mL of NH4OH (1 + 1) in excess. Heat
from the CO2 of the air by means of a guard tube packed with
to boiling, filter on medium-textured paper and wash with
Ascarite. Standardize against standard acid phthalate such as
diluted NH4OH (5 + 95). Discard the filtrate.
NIST Standard Sample No. 84 or benzoic acid, NIST Standard
Sample No. 39 furnished by the National Institute of Standards NOTE X3.3—Small amounts of phosphorus in the sample can be
and Technology4 , as follows: concentrated very easily this way. The iron combines with the phosphate
to form FePO4 that is very insoluble in NH4OH and affords the analyst the
NOTE X3.1—Ba(OH)2 precipitates the carbonate as insoluble BaCO3. opportunity to separate it from major matrix elements.
X3.3.3.1 Lightly crush 5 to 6 g of standard acid potassium X3.4.2 Place the precipitating beaker under the funnel and
phthalate to a fineness of approximately 10 mesh and dry for punch a small hole in the tip of the filter cone by pushing a
2 h at 100°C. Place in a small glass-stoppered container and platinum wire through it. Pour 25 mL of hot HNO3 (1 + 4)
cool in a desiccator. through the paper and wash free of iron with hot 5 % HNO3.
X3.3.3.2 Accurately weigh about 1 g of the dried standard Discard the paper.
and transfer it to a 500-mL Erlenmeyer flask. X3.4.3 Evaporate the nitric acid of solution to dryness and
X3.3.3.3 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. Add 3 drops of phenolphthalein indicator HNO3 + 40 mL HCl (1 + 1). Boil on hot plate until reddish-
and titrate with the sodium hydroxide to the first pink color. brown fumes cease to come off and for several minutes
X3.3.3.4 Calculate the normality of NaOH as follows: thereafter. Add 100 mL of water and boil.
N 5 W/V 3 204.228 (X3.1) X3.4.4 Filter into a 500-mL Erlenmeyer flask and wash with
hot water. Ignite the residue, cool, add 1 mL of HNO3 and
where:
10 mL of HF and evaporate to dryness (see Note X3.4).
N = normality of NaOH solution, Evaporate twice with nitric acid to expel all the HF. Fuse
W = grams of potassium acid phthalate, residue with a pinch of Na2CO3 (0.5 g), dissolve in dilute nitric
V = millilitres of NaOH used, and
acid, and add to the filtrate in the Erlenmeyer flask.
204.228 = gram equivalent weight of potassium acid
phthalate. NOTE X3.4—The treatment of the residue with HF and HNO3 may be
omitted if the SiO2 in the sample is low, <3 %.
X3.3.3.5 Calculate the phosphorus pentoxide (P2O5)
equivalent (see Note X3.2) of the NaOH solution in grams per X3.4.5 Neutralize the nitric acid solution with NH4OH until
millilitre as follows: iron hydroxide just begins to form. Reacidify with nitric acid
slowly until precipitate just dissolves, then add 1 mL of HNO3
E 5 N 3 0.003086 (X3.2)
for every 100 mL of solution. Heat the solution to 40°C and
where: add 40 mL of ammonium molybdate ((NH4)2MoO4) (filtered).
E = P2O5 equivalent of the NaOH solution, g/mL, Stopper the flask, shake for several minutes, and allow to settle
N = normality of the NaOH solution, and overnight (12 h).
0.003086 = P2O5 equivalent of 1 N NaOH solution, g/mL. X3.4.6 Filter through a retentive paper. Wash the flask and
NOTE X3.2—Phosphorus reacts to form ammonium phosphomolybdate precipitate five times with 15-mL portions of a 1 % solution of
2(NH4)3PO4 · 12MoO3. 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 =
of the same solution. The paper should be carefully washed
2(NH4)2HPO4 + (NH4)2MoO4 + 23Na2MoO4 + 22H2O each time from the rim downward and then allowed to drain
The equivalent weight of P2O5 (0.003086) is obtained by completely before washing with the next portion of wash
dividing the molecular weight of P2O5 (141.96) by 46 (for 46 solution. (The wash solution must be free of CO2.)
moles of NaOH in the equation) and by 1000 (number of X3.4.7 Return the paper and precipitate to the flask, add
millilitres in 1 L). As the actual composition of the precipitate about 75 mL of CO2-free water, and add enough standard
is influenced by the conditions under which the precipitation is sodium hydroxide solution to decompose the precipitate and
made, it is essential that all the details of the procedure be leave approximately 2 mL in excess. Record the millilitres of
followed closely as prescribed. NaOH solution added.
X3.3.4 Sulfuric Acid, Standard (0.15 N)—Dilute 4.0 mL of X3.4.8 Stopper the flask and shake to disintegrate the paper.
H2SO4 to 1 L with water that has been freshly boiled and Wash the stopper and sides of the flask with CO2-free water,
cooled. Standardize against the standard NaOH solution. De- add 6 drops of phenolphthalein indicator solution, 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. Record the millilitres of
solution by the volume of H2SO4 solution used in titration. standard acid.
35
C25 − 17
X3.5 Calculation: V1 = NaOH solution used, mL,
NOTE X3.5—Titanium and vanadium interfere in this determination but V2 = H2SO4 solution used, mL,
should not be encountered in significant amounts in this class of material. R = ratio in strength of the NaOH solution to the H2SO4
X3.5.1 Calculate the percent P2O5 as follows: solution, and
W = mass of sample, g.
P 2 O 5 , % 5 $ E ~ V 1 2 V 2 R ! % /W 3 100 (X3.3)
X3.6 Precision and Bias—The precision and bias of this
where: method have not been determined.
E = P2O5 equivalent of the NaOH solution, g/mL,
X4. MANGANESE BY THE BISMUTHATE METHOD
X4.1 Scope—This is the standard titrimetric method that X4.5 Procedure:

may be used to determine manganese in lime and limestone X4.5.1 Dissolve 10 g of the sample in 100 mL of diluted
samples when the concentration of manganese is at least HNO3 (1 + 1), filter, and wash the residue with hot water.
0.05 %. Ignite the residue in platinum, fuse with a little Na2CO3, and
X4.2 Summary of Test Method—After dissolution of the add the nitric acid solution of the melt to the main filtrate.
sample, bivalent manganese is oxidized to permanganic acid X4.5.2 Dilute the solution to 150 mL and add 0.5 g of
by the use of sodium bismuthate (NaBiO3) in nitric acid sodium bismuthate. Heat for a few minutes or until the pink
solution, filtering, washing with nitric acid, adding a measured color has disappeared and MnO2 has precipitated. If MnO2
excess of ferrous sulfate and then determining this excess by does not precipitate, add more bismuthate.
titration with a standard solution of permanganate. X4.5.3 Clear the solution by slowly adding ferrous ammo-
nium sulfate solution (12 g/L) until the MnO2 dissolves. Boil to
X4.3 Apparatus:
expel brown fumes, cool to 10 to 15°C, add 0.5 to 1.5 g of
X4.3.1 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. manganese present), and agitate vigorously for 1 min. Add 50
mL of cold HNO3 (3 + 97) and filter through a Gooch crucible
X4.4 Reagents:
or fritted glass crucible of fine porosity. Wash with 50 mL of
X4.4.1 Sodium Bismuthate—The sodium bismuthate shall cold HNO3 (3 + 97) or until the washings run colorless.
contain enough active oxygen to correspond to at least 75 % X4.5.4 Add enough ferrous ammonium sulfate solution (12
NaBiO3. g/L) from a buret to discharge completely the permanganate
X4.4.2 Ferrous Ammonium Sulfate Solution (12 g/L)— color and then add 1.0 to 2.0 mL in excess. Record the buret
Dissolve 12 g of Fe(NH4)2(SO4)2 · 6H2O in 1 L of cool H2SO4 reading. Titrate the excess ferrous with 0.05 N KMnO4 solution
(5 + 95). to a faint pink end point.
X4.4.3 Standardization of Ferrous Ammonium Sulfate X4.6 Calculation—Calculate the percentage of manganese
Solution—Measure into a 250-mL Erlenmeyer flask, 50 mL of as follows:
cold nitric acid (3 + 97). Add about 0.5 g of sodium bismuthate
(NaBiO3), agitate, dilute with 50 mL of HNO3 (3 + 97) and
filter through asbestos or a fritted glass crucible. To the filtrate Mn, % 5 ~ V 1 R 2 V 2 ! N/W 3 1.0988 (X4.1)
add 50 mL of the ferrous ammonium sulfate solution and titrate where:
with standard KMnO4 solution to pink color. Determine the V1 = Fe(NH4)2(SO4)2 solution used, mL,
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,
KMnO4 solution by the volume of Fe(NH4)2(SO4)2 solution V2 = KMnO4 solution used, mL,
used in the titration. N = normality of KMnO4 solution,
X4.4.4 Nitric Acid (3 + 97). W = mass of sample, g, and
1.0988 = manganese equivalent of KMnO4 × 100.
X4.4.5 Potassium Permanganate Standard Solution
(0.05 N)—The same solution as prepared in the Total Iron, X4.7 Precision and Bias—The precision and bias of this test
Standard Method, Section 13. method have not been determined.
36
C25 − 17
X5. FERROUS IRON BY TITRATION WITH POTASSIUM PERMANGANATE
X5.1 Scope—The determination of ferrous iron in carbonate iron is exceedingly slow. It is ordinarily quite sufficient to equalize the
rocks is difficult if not impossible in the presence of carbona- internal and external pressures by opening the cock, removing the stopper,
and pouring in cold water.
ceous matter. Nevertheless, acceptable results are sometimes
NOTE X5.3—If MnO2 is absent, the potassium dichromate method of
obtainable if there is not much of such matter, and if it does not titration may be substituted and HCl used instead of H2SO4. In this case,
give a colored solution with acid. But even then, it is only the there is no separation of an insoluble calcium salt which renders easier the
soluble iron, existing chiefly if not wholly as carbonate, that is subsequent determination of iron in the insoluble residue.
determinable. X5.4.2 Ferrous Iron in the Insoluble Residue in Absence of
Carbonaceous Matter:
X5.2 Summary of Test Method—The limestone sample is
decomposed with dilute sulfuric acid in a steam or CO2 X5.4.2.1 Filter the titrated solution (see X5.4.1.1) through a
atmosphere and the soluble ferrous iron is titrated with medium-sized, hardened filter. Transfer the residue completely
KMnO4. In the absence of carbonaceous matter, it is possible to the paper and wash with hot water. Rinse the contents of the
to determine ferrous iron in the insoluble residue. Metallic iron, paper into a large platinum crucible (80 to 100-mL capacity)
if introduced by grinding media, will also be determined as with a snugly fitting cover of transparent polypropylene and
ferrous iron, and precautions should be taken to avoid this having a plastic tube for the introduction of CO2 and a small
contaminate. plastic funnel for the addition of acid and the escape of vapors
and steam.
X5.3 Special Solutions: X5.4.2.2 Add 18 mL of H2SO4 (1 + 1) and air-free water
until the crucible is at least half full. Drop in a small coil of
X5.3.1 Potassium Permanganate, Standard Solution (0.05
platinum wire to prevent bumping, fit the cover tightly, and
N)—Prepare as in Total Iron, Standard Method (see Section
pass CO2 through for at least 10 min as the mixture is gradually
13).
brought to boiling. Stop the stream of gas as soon as steam
X5.3.2 Diphenylamine Sulfonate Indicator Solution— escapes, immediately add 7 mL of HF through the funnel, and
Dissolve 0.2 g of sodium diphenylamine sulfonate in 100 mL boil gently for 10 to 15 min, or until decomposition is
of water. complete.
X5.3.3 Potassium Dichromate, Standard Solution (0.028 X5.4.2.3 Prepare an 800-mL beaker containing 500 mL of
N)—Weigh 2.728 g of dry National Institute of Standards and air-free water, 12 g of boric acid, and 20 mL of H2SO4 (1 + 3).
Technology potassium dichromate (K2Cr2O7) or other pure, Quickly transfer the crucible cover and contents to the 800-mL
dry K2Cr2O7 and dilute to 2 L in a volumetric flask. The beaker. With the aid of a stirring rod, remove the crucible and
solution contains the equivalent of 0.002 g FeO/mL. cover from the beaker and rinse it off with water. Add 3 to 5
drops of sodium diphenylamine sulfonate indicator and titrate
X5.4 Procedure: with the K2Cr2O7 standard solution to a purple color that
X5.4.1 In Absence of Carbonaceous Matter: persists for 20 to 30 s.
X5.4.1.1 Weigh several grams of prepared sample into a NOTE X5.4—Potassium dichromate is preferred because it reacts much
flask of about 250-mL capacity, add 25 mL of water, and boil less rapidly on organic matter than permanganate.
water until air is expelled. While still boiling, add diluted X5.4.3 Ferrous Iron in Presence of Insoluble Carbonaceous
H2SO4 (1 + 1) a little at a time until effervescence ceases, then Matter:
add a few millilitres in excess (see Note X5.1). Calcium sulfate X5.4.3.1 Weigh 2 to 5 g of prepared sample into a flask of
precipitates, but the iron will remain in solution. Remove the about 250-mL capacity, 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. When the flask is cool, or nearly so, pour cold cence ceases, then add a few more millilitres in excess. Heat if
water into the funnel and cautiously open the cock so the water necessary to decompose the limestone (see Note X5.5) and
may be drawn into the flask. Keep filling the funnel as fast as filter quickly (see Note X5.6) through asbestos or sintered glass
it empties until the solution in the flask amounts to 100 to fiber (in an atmosphere of carbon dioxide if much iron is
150 mL (see Note X5.2). Immediately titrate the iron solution present). Wash the filter and the residue a few times with water
in the flask with 0.05 N KMnO4 solution (see Note X5.3). The and titrate the filtrate at once with 0.05 N KMnO4 solutions.
ferrous iron thus found is mostly, if not altogether, that existing Discard the residue (see Note X5.7).
as carbonate.
Warning—The contents of the flask may erupt violently NOTE X5.5—Heat is not needed with limestone if active agitation is
used; but with dolomites, heat is necessary.
unless this addition is made with care.
NOTE X5.6—It is important to allow the acid to act no longer than is
NOTE X5.1—With a carbonate that is wholly decomposable without the necessary and to filter quickly.
aid of heat, solution may be accomplished in a flask filled with CO2, using NOTE X5.7—A determination of the ferrous iron in the insoluble matter
cold acid. This mode of acid decomposition lessens the danger of is usually not worth attempting because of the admixed organic matter.
attacking silicates if these are present.
NOTE X5.2—Such precaution to exclude air is hardly necessary, in most X5.5 Calculation—Calculate the percent FeO as follows:
cases; however, since in the presence of H2SO4 the oxidation of ferrous
37
C25 − 17
FeO, % 5 V 3 N 3 7.184/W (X5.1) W = weight of sample, g, and
where: 7.184 = equivalent weight of FeO × 100.
V = titrant (KMnO4 or K2Cr2O7), mL, X5.6 Precision and Bias—The precision and bias of this test
N = normality of KMnO4 or K2Cr2O7 solution, method have not been determined.
X6. TEST METHOD FOR FREE CALCIUM OXIDE IN HIGH-CALCIUM HYDRATED LIME10
X6.1 Scope X6.4 Procedure

X6.1.1 This test method covers the determination of the X6.4.1 Weigh a clean, dry, 10-mL Erlenmeyer flask on an
amount of free calcium oxide (CaO) in high-calcium hydrated analytical balance.
lime capable of being hydrated by steam at atmospheric NOTE X6.1—Once started, complete the test without interruption.
pressure.
X6.4.2 Add to the flask, by means of a widestem funnel, 3
X6.2 Summary of Test Method to 5 g of the lime to be tested. Reweigh to get the exact sample
weight.
X6.2.1 This test method is based on the principle of gain in
weight of CaO when it is hydrated to form calcium hydroxide NOTE X6.2—The flask should be kept stoppered at all times, except
(Ca(OH)2). when weighing, drying, or steaming.
X6.2.2 The sample is dried, subjected to steam at atmo- X6.4.3 Place the flask in the drying oven that has been
spheric pressure, again dried, and the gain in weight calculated previously heated to 120°C, and maintain at this temperature
to CaO. for 30 min. Remove, stopper, cool in a desiccator, and weigh.
NOTE X6.3—Oven atmosphere can be kept CO2 free by placing therein
X6.3 Apparatus a container of soda lime, quicklime, or other suitable CO2-absorbing
X6.3.1 Drying Oven, thermostatically controlled, CO2-free medium.
atmosphere. X6.4.4 Place the flask and the sample in a vigorously
boiling steam bath and steam for 30 min. Protect the flask in
X6.3.2 Analytical Balance.
the steam bath by a drip shield during the steaming period.
X6.3.3 Steam Bath, as shown in Fig. X6.1. Remove the flask to the oven, dry for 30 min at 120°C, stopper,
cool in a desiccator, and weigh.
10
This test method was taken from the Appendix of Specification C911. X6.4.5 Record all weighings to the fourth decimal place.
FIG. X6.1 Steam Chamber
38
C25 − 17
X6.5 Calculation where:
X6.5.1 Calculate the percentage of water and CaO as W1 = weight of sample and flask before drying,
follows: W2 = weight of sample and flask after drying,
W3 = weight of sample and flask after steaming and drying,
Free water, % 5 @ ~ W 1 2 W 2 ! /S # 3 100 (X6.1)
and
~ W 3 2 W 2 ! 3 3.114 S = weight of sample.
Free CaO, % 5 3 100
S
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Chemical Analysis of Limestone, Quicklime, and Hydrated Lime

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Chemical Analysis of Limestone, Quicklime, and Hydrated Lime

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This international standard was developed in accordance with internationally recognized principles on standardization established in the Decision on Principles

Standard Test Methods for

1. Scope Insoluble Matter Other Than Silicon Dioxide 11

TABLE 2 Approved SRM List

TABLE 3 Precision Summary of Classical Test Methods

Precision Statement for 16.3.2 Ammonium Oxalate Wash Solution (1 g/L)—

A Soda-Lime Tower at inlet to remove CO2.

TABLE 5 Test Result (Wt%)

A Purifying jar, Fleming, containing concentrated H2SO4.

A 5 B/ ~ 0.121136 3 C ! (26) 28.4.2 Procedure for Hydrated Lime—The procedure for

5.0045 ~ V 1 N 1 2 V 2 N 2 ! 34.4 Special Solutions:

HISTORICAL ASTM METHODS

X1. TOTAL IRON BY THE POTASSIUM PERMANGANATE TITRATION METHOD

X2. STRONTIUM OXIDE BY THE GRAVIMETRIC SULFATE (ETHER) METHOD

X3. PHOSPHORUS BY THE TITRIMETRIC METHOD

X4. MANGANESE BY THE BISMUTHATE METHOD

X4.1 Scope—This is the standard titrimetric method that X4.5 Procedure:

X5. FERROUS IRON BY TITRATION WITH POTASSIUM PERMANGANATE

X6.1 Scope X6.4 Procedure

FIG. X6.1 Steam Chamber

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