ASTM E465-23

Standard Test Methods for Determination of Manganese (IV) in Manganese Ores by Redox Titrimetry

SIGNIFICANCE AND USE
4.1 This test method is intended to be used for compliance with compositional specifications for manganese dioxide content in manganese ores. It is assumed that all who use these procedures will be trained analysts capable of performing common laboratory procedures skillfully and safely. It is expected that work will be performed in a properly equipped laboratory and that proper waste disposal procedures will be followed. Appropriate quality control practices shall be followed, such as those described in Guide E882.
SCOPE
1.1 These test methods cover the determination of manganese dioxide in amounts commonly found in manganese ore. The determination measures the amount of manganese (IV) present in the sample. The result may be expressed as available oxygen or as manganese dioxide. The following test methods are included and may be used interchangeably:    
Sections  
Test Method A (Ferrous Ammonium Sulfate)  
9 – 13  
Test Method B (Periodate (Sodium Oxalate)  
14 – 18  
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety, health, and environmental practices and determine the applicability of regulatory limitations prior to use.  
1.4 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.

General Information

• Status: Published
• Publication Date: 31-Mar-2023
• ICS: 73.060.20 - Manganese ores
• Technical Committee: E01 - Analytical Chemistry for Metals, Ores, and Related Materials
• Drafting Committee: E01.02 - Ores, Concentrates, and Related Metallurgical Materials

Relations

• Refers: ASTM E135-20 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Jan-2020
• Refers: ASTM E135-19 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-May-2019
• Refers: ASTM E50-17 - Standard Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
• Effective Date: 01-Sep-2017
• Refers: ASTM E882-10(2016)e1 - Standard Guide for Accountability and Quality Control in the Chemical Analysis Laboratory
• Effective Date: 01-Dec-2016
• Refers: ASTM E882-10(2016) - Standard Guide for Accountability and Quality Control in the Chemical Analysis Laboratory
• Effective Date: 01-Dec-2016
• Refers: ASTM E50-11(2016) - Standard Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
• Effective Date: 01-Aug-2016
• Refers: ASTM E135-16 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-May-2016
• Refers: ASTM E135-15a - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Jul-2015
• Refers: ASTM E135-15 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-May-2015
• Refers: ASTM E135-14b - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-Aug-2014
• Refers: ASTM E135-14a - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Apr-2014
• Refers: ASTM E135-14 - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-Feb-2014
• Refers: ASTM E135-13a - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 01-Dec-2013
• Refers: ASTM E50-11 - Standard Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
• Effective Date: 15-Oct-2011
• Refers: ASTM E135-11b - Standard Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• Effective Date: 15-Sep-2011

Overview

ASTM E465-23 is the international standard developed by ASTM for the determination of manganese (IV) in manganese ores using redox titrimetry. This standard specifies test methods for the quantitative measurement of manganese dioxide content, a key component used as a quality metric in manganese ores. The procedures described are essential for ensuring compliance with compositional specifications in various industrial and laboratory settings. The standard emphasizes proper laboratory practices, including safety, quality control, and accurate reporting using SI units.

Key Topics

• Scope of Application:

  • These test methods are designed for analyzing manganese dioxide levels typically found in manganese ore samples.
  • The results may be reported as either available oxygen or manganese dioxide content.

• Test Methods:

  • Test Method A (Ferrous Ammonium Sulfate Method):
    • Involves reacting the sample with ferrous ammonium sulfate and titrating the excess iron with potassium dichromate.
  • Test Method B (Sodium Oxalate Method):
    • Uses sodium oxalate and titration with potassium permanganate to determine excess oxalate.
  • Both methods are interchangeable and provide reliable results for manganese (IV) determination.

• Laboratory Practices:

  • Requires skilled analysts trained in chemical procedures and laboratory safety.
  • Calls for use of high-purity reagents and adherence to best quality control practices, such as those specified in ASTM E882.
  • The standard underscores the importance of proper waste management and regulatory compliance.

• Precision and Quality Control:

  • The methods outlined have demonstrated precision in interlaboratory studies.
  • Users are encouraged to utilize reference materials for method validation and bias assessment, ensuring reliable manganese dioxide analysis.

Applications

• Mining and Metallurgy:

  • Used in the quality assessment and grading of manganese ore for industrial processes.
  • Supports compliance with purchasing specifications and regulatory requirements for manganese oxide content.

• Quality Control Laboratories:

  • Essential for laboratories conducting routine analysis of ore compositions.
  • Enables reliable reporting of manganese dioxide concentrations to meet industry standards.

• Research and Development:

  • Valuable for research in geology and material science focusing on manganese ore characterization.
  • Supports method comparison and validation studies due to the inclusion of two alternative titrimetric procedures.

• Environmental and Regulatory Compliance:

  • Helps organizations demonstrate adherence to international trade and environmental regulations by establishing accurate material compositions.

Related Standards

For comprehensive chemical analysis and laboratory practices, ASTM E465-23 references several related standards, including:

• ASTM D1193: Specification for Reagent Water
• ASTM E29: Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
• ASTM E50: Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
• ASTM E135: Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
• ASTM E882: Guide for Accountability and Quality Control in the Chemical Analysis Laboratory

Practical Value

ASTM E465-23 offers practical, standardized approaches for analyzing manganese dioxide content in ores. By following these methods, laboratories and industries can ensure product quality, regulatory compliance, and accuracy in the chemical composition of manganese ore. This standard is a critical resource for professionals involved in material testing, quality control, and compliance in the mining and metallurgical sectors.

Standards Content (Sample)

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: E465 − 23
Standard Test Methods for
Determination of Manganese (IV) in Manganese Ores by
Redox Titrimetry
This standard is issued under the fixed designation E465; 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.
1. Scope erations for Chemical Analysis of Metals, Ores, and
Related Materials
1.1 These test methods cover the determination of manga-
E135 Terminology Relating to Analytical Chemistry for
nese dioxide in amounts commonly found in manganese ore.
Metals, Ores, and Related Materials
The determination measures the amount of manganese (IV)
E882 Guide for Accountability and Quality Control in the
present in the sample. The result may be expressed as available
Chemical Analysis Laboratory
oxygen or as manganese dioxide. The following test methods
are included and may be used interchangeably:
3. Terminology
Sections
3.1 Definitions—For definitions of terms used in this test
Test Method A (Ferrous Ammonium Sulfate) 9 – 13
method, refer to Terminology E135.
Test Method B (Periodate (Sodium Oxalate) 14 – 18
1.2 The values stated in SI units are to be regarded as
4. Significance and Use
standard. No other units of measurement are included in this
4.1 This test method is intended to be used for compliance
standard.
with compositional specifications for manganese dioxide con-
1.3 This standard does not purport to address all of the
tent in manganese ores. It is assumed that all who use these
safety concerns, if any, associated with its use. It is the
procedures will be trained analysts capable of performing
responsibility of the user of this standard to establish appro-
common laboratory procedures skillfully and safely. It is
priate safety, health, and environmental practices and deter-
expected that work will be performed in a properly equipped
mine the applicability of regulatory limitations prior to use.
laboratory and that proper waste disposal procedures will be
1.4 This international standard was developed in accor-
followed. Appropriate quality control practices shall be
dance with internationally recognized principles on standard-
followed, such as those described in Guide E882.
ization established in the Decision on Principles for the
Development of International Standards, Guides and Recom-
5. Interferences
mendations issued by the World Trade Organization Technical
5.1 The elements ordinarily present in manganese ores do
Barriers to Trade (TBT) Committee.
not interfere in either test method.
2. Referenced Documents
6. Reagents and Materials
2.1 ASTM Standards:
6.1 Purity of Reagents—Reagent grade chemicals shall be
D1193 Specification for Reagent Water
used in all tests. Unless otherwise indicated, it is intended that
E29 Practice for Using Significant Digits in Test Data to
all reagents conform to the specifications of the Committee on
Determine Conformance with Specifications
Analytical Reagents of the American Chemical Society where
E50 Practices for Apparatus, Reagents, and Safety Consid-
such specifications are available. Other grades may be used,
provided it is first ascertained that the reagent is of sufficient
high purity to permit its use without lessening the accuracy of
These test methods are under the jurisdiction of ASTM Committee E01 on
Analytical Chemistry for Metals, Ores, and Related Materials and are the direct
the determination.
responsibility of Subcommittee E01.02 on Ores, Concentrates, and Related Metal-
lurgical Materials.
Current edition approved April 1, 2023. Published April 2023. Originally
approved in 1972. Last previous edition approved in 2017 as E465 – 11 (2017). ACS Reagent Chemicals, Specifications and Procedures for Reagents and
DOI: 10.1520/E0465-23. Standard-Grade Reference Materials, American Chemical Society, Washington,
For referenced ASTM standards, visit the ASTM website, www.astm.org, or DC. For suggestions on the testing of reagents not listed by the American Chemical
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Society, see Analar Standards for Laboratory Chemicals, BDH Ltd., Poole, Dorset,
Standards volume information, refer to the standard’s Document Summary page on U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharma-
the ASTM website. copeial Convention, Inc. (USPC), Rockville, MD.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E465 − 23
6.2 Purity of Water—Unless otherwise indicated, references 150 mL with cold water (from which the air was removed by
to water shall be understood to mean reagent water conforming boiling) and titrate the excess ferrous ammonium sulfate with
to Type I or II of Specification D1193. Type III or IV may be standard K Cr O solution to a permanent purple end point.
2 2 7
used if they effect no measurable change in the blank or
11.6 The correlation between the solutions of ferrous am-
sample.
monium sulfate and potassium dichromate is established under
test conditions. For this purpose, transfer into a flask the same
7. Hazards
amount of ferrous ammonium sulfate solution used to dissolve
7.1 For precautions to be observed in these methods, refer to
the ore, and proceed as directed in 11.3.
Practice E50.
12. Calculation
8. Sampling and Sample Preparation
12.1 Calculate the manganese dioxide content as follows:
8.1 The sample shall pass a No. 100 (150-μm) sieve.
@~A 2 B! × C × 4.3465#
Manganese dioxide, % 5 (1)
TEST METHOD A—FERROUS AMMONIUM
D
SULFATE METHOD
where:
9. Summary of Test Method
A = millilitres of standard K Cr O solution used to estab-
2 2 7
lish the correlation in 11.6,
9.1 The test sample is dissolved in an excess of ferrous
B = millilitres of standard K Cr O solution required to
2 2 7
ammonium sulfate solution. The manganese dioxide reacts
titrate the excess of ferrous ammonium sulfate in the
with an equivalent amount of ferrous iron. The excess ferrous
sample solution,
iron is titrated with standard potassium dichromate solution
C = the normality of standard K Cr O solution, and
2 2 7
using sodium diphenylamine sulfonate as an indicator.
D = grams of test sample used.
NOTE 1—As used in this test method (except as related to the term
10. Reagents and Materials
relative standard deviation), “percent” or “%” refers to mass fraction
10.1 Ferrous Ammonium Sulfate Solution (45 g/L)—
(wt/wt) of the form g/100g.
Dissolve 45 g of ferrous ammonium sulfate
12.2 Rounding of test results obtained using this test method
[Fe(NH ) (SO ) ·6H O] in 1 L of H SO , (1 + 7).
4 2 4 2 2 2 4
shall be performed in accordance with Practice E29, Rounding
10.2 Potassium Dichromate, Standard Solution (0.1 N)
Method, unless an alternative rounding method is specified by
10.2.1 Dissolve 4.9035 g of Primary Standard Grade potas-
the customer or applicable material specification.
sium dichromate (K Cr O ) in water, transfer to a 1-L volu-
2 2 7
13. Precision and Bias
metric flask, dilute to volume, and mix.
10.3 Sodium Diphenylamine Sulfonate Indicator Solution, 13.1 Precision—Table 1 indicates the precision of the test
method between laboratories.
(2 g/L).
10.3.1 Dissolve 0.20 g of sodium diphenylamine sulfonate
13.2 Bias—No information on the bias of this test method is
in 100 mL of water. Store in a dark-colored bottle.
known. Accepted reference materials may have not been
included in the materials used in the interlaboratory study.
11. Procedure
Users of the method are encouraged to employ accepted
11.1 Transfer approximately 0.4 g of test sample to a small,
reference materials, if avai
...

This document is not an ASTM standard and is intended only to provide the user of an ASTM standard an indication of what changes have been made to the previous version. Because
it may not be technically possible to adequately depict all changes accurately, ASTM recommends that users consult prior editions as appropriate. In all cases only the current version
of the standard as published by ASTM is to be considered the official document.
Designation: E465 − 11 (Reapproved 2017) E465 − 23
Standard Test Methods for
Determination of Manganese (IV) in Manganese Ores by
Redox Titrimetry
This standard is issued under the fixed designation E465; 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.
1. Scope
1.1 These test methods cover the determination of manganese dioxide in amounts commonly found in manganese ore. The
determination measures the amount of manganese (IV) present in the sample. The result may be expressed as available oxygen
or as manganese dioxide. The following test methods are included and may be used interchangeably:
Sections
Test Method A (Ferrous Ammonium Sulfate) 9 – 13
Test Method B (Periodate (Sodium Oxalate) 14 – 18
1.2 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.
1.3 This standard does not purport to address all of the safety concerns, if any, associated with its use. It is the responsibility
of the user of this standard to establish appropriate safety and healthsafety, health, and environmental practices and determine
the applicability of regulatory limitations prior to use.
1.4 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.
2. Referenced Documents
2.1 ASTM Standards:
D1193 Specification for Reagent Water
E29 Practice for Using Significant Digits in Test Data to Determine Conformance with Specifications
E50 Practices for Apparatus, Reagents, and Safety Considerations for Chemical Analysis of Metals, Ores, and Related Materials
E135 Terminology Relating to Analytical Chemistry for Metals, Ores, and Related Materials
E882 Guide for Accountability and Quality Control in the Chemical Analysis Laboratory
3. Terminology
3.1 Definitions—For definitions of terms used in this test method, refer to Terminology E135.
These test methods are under the jurisdiction of ASTM Committee E01 on Analytical Chemistry for Metals, Ores, and Related Materials and are the direct responsibility
of Subcommittee E01.02 on Ores, Concentrates, and Related Metallurgical Materials.
Current edition approved May 1, 2017April 1, 2023. Published June 2017April 2023. Originally approved in 1972. Last previous edition approved in 20112017 as E465
– 11. DOI: 10.1520/E0465-11R17.11 (2017). DOI: 10.1520/E0465-23.
For referenced ASTM standards, visit the ASTM website, www.astm.org, or contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
E465 − 23
4. Significance and Use
4.1 This test method is intended to be used for compliance with compositional specifications for manganese dioxide content in
manganese ores. It is assumed that all who use these procedures will be trained analysts capable of performing common laboratory
procedures skillfully and safely. It is expected that work will be performed in a properly equipped laboratory and that proper waste
disposal procedures will be followed. Appropriate quality control practices shall be followed, such as those described in Guide
E882.
5. Interferences
5.1 The elements ordinarily present in manganese ores do not interfere in either test method.
6. Reagents and Materials
6.1 Purity of Reagents—Reagent grade chemicals shall be used in all tests. Unless otherwise indicated, it is intended that all
reagents conform to the specifications of the Committee on Analytical Reagents of the American Chemical Society where such
specifications are available. Other grades may be used, provided it is first ascertained that the reagent is of sufficient high purity
to permit its use without lessening the accuracy of the determination.
6.2 Purity of Water—Unless otherwise indicated, references to water shall be understood to mean reagent water conforming to
Type I or II of Specification D1193. Type III or IV may be used if they effect no measurable change in the blank or sample.
7. Hazards
7.1 For precautions to be observed in these methods, refer to Practice E50.
8. Sampling and Sample Preparation
8.1 The sample shall pass a No. 100 (150-μm) sieve.
TEST METHOD A—FERROUS AMMONIUM SULFATE METHOD
9. Summary of Test Method
9.1 The test sample is dissolved in an excess of ferrous ammonium sulfate solution. The manganese dioxide reacts with an
equivalent amount of ferrous iron. The excess ferrous iron is titrated with standard potassium dichromate solution using sodium
diphenylamine sulfonate as an indicator.
10. Reagents and Materials
10.1 Ferrous Ammonium Sulfate Solution (45 g/L)—Dissolve 45 g of ferrous ammonium sulfate [Fe(NH ) (SO ) ·6H O] in 1 L
4 2 4 2 2
of H SO , (1 + 7).
2 4
10.2 Potassium Dichromate, Standard Solution (0.1 N)
10.2.1 Dissolve 4.9035 g of Primary Standard Grade potassium dichromate (K Cr O ) in water, transfer to a 1-L volumetric flask,
2 2 7
dilute to volume, and mix.
10.3 Sodium Diphenylamine Sulfonate Indicator Solution, (2 g/L).
10.3.1 Dissolve 0.20 g of sodium diphenylamine sulfonate in 100 mL of water. Store in a dark-colored bottle.
Reagent Chemicals, American Chemical Society Specifications,ACS Reagent Chemicals, Specifications and Procedures for Reagents and Standard-Grade Reference
Materials, American Chemical Society, Washington, DC. For suggestions on the testing of reagents not listed by the American Chemical Society, see Analar Standards for
Laboratory Chemicals, BDH Ltd., Poole, Dorset, U.K., and the United States Pharmacopeia and National Formulary, U.S. Pharmacopeial Convention, Inc. (USPC),
Rockville, MD.
E465 − 23
11. Procedure
11.1 Transfer approximately 0.4 g of test sample to a small, dry weighing bottle and place into a drying oven. Dry at 120 °C for
1 h, cap the bottle, and cool to room temperature in a desiccator. Momentarily release the cap to equalize the pressure and weigh
the capped bottle to the nearest 0.1 mg. Repeat the drying and weighing until there is no further mass loss. Transfer the test sample
to a dry 300-mL Erlenmeyer flask and reweigh the capped bottle to the nearest 0.1 mg. The difference is the mass of the test sample.
11.2 Add 50.0 mL of the ferrous ammonium sulfate solution, plus an additional 10.0 mL for each 0.1 g of MnO present, to the
flask. Close the flask with a stopper equipped with inlet and outlet tubes. Pass carbon dioxide (CO ) through the flask.
11.3 Heat the flask moderately and shake intermittently until the ore is decomposed.
11.4 Cool the contents of the flask while maintaining the flow of carbon dioxide.
11.5 UnstopperOpen the flask, add 2 mL of sodium diphenylamine sulfonate indicator solution, and 10 mL of H PO . Dilute to
3 4
150 mL with cold water (from which the air was removed by boiling) and titrate the excess ferrous ammonium sulfate with
standard K Cr O solution to a permanent purple end point.
2 2 7
11.6 The correlation between the solutions of ferrous ammonium sulfate and potassium dichromate is established under test
conditions. For this purpose, transfer into a flask the same amount of ferrous ammonium sulfate solution used to dissolve the ore,
and proceed as directed in 11.3.
12. Calculation
12.1 Calculate the manganese dioxide content as follows
...