D16.12 - Caustics and Peroxides

SIGNIFICANCE AND USE
4.1 Hydroxyl is an important functional group, and knowledge of its content is required in many intermediate and end use applications. The test methods described herein are for the determination of primary and secondary hydroxyl groups and can be used for the assay of compounds containing them.
SCOPE
1.1 These test methods cover the determination of hydroxyl groups attached to primary and secondary carbon atoms in aliphatic and alicyclic compounds and phenols.  
1.2 Three test methods are given as follows:    
Sections  
Test Method A (Pressure Bottle Method)  
8 – 14    
Test Method B (Reflux Method)  
16 – 22    
Test Method C (Perchloric Acid Catalyzed Method)  
24 – 30  
1.2.1 Test Method A is recommended for general use. Test Method B is included to give a standard procedure for the method that has been used widely. Test Method C is recommended when the results are required in a minimum period of time or where ambient temperature for the reaction is desired.  
1.2.2 The results obtained using Test Methods A and B will be essentially the same, but the results obtained using Test Method C will be higher (up to approximately 4 % relative) than those obtained using the other two methods.  
1.2.3 Statements on precision are included with each test method. The precision of Test Methods A and C is consistent over a wide range of hydroxyl content (tested over hydroxyl number range of 250 to 1600), whereas Test Method B is less precise at the higher hydroxyl content level than it is at the lower hydroxyl content level. In general, Test Method A is approximately two-fold as precise as Test Method C. Test Method B has approximately the same precision as Test Method C at the lower hydroxyl content level but poorer precision at the higher hydroxyl content level.  
1.2.4 The interferences are essentially the same for the three methods. Some compounds can be analyzed using Test Methods A or B but not using Test Method C because of interfering reactions of the strong acid catalyst with the compound being analyzed or the acetate product formed in the determination. However, because of its increased reactivity, Test Method C is applicable for determination of some compounds, particularly sterically hindered secondary alcohols, which react too slowly or not at all in Test Methods A and B.
Note 1: Other methods for determination of hydroxyl groups are given in Test Methods D1957, D2195, E326, E335, and E567.  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 In determining the conformance of the test results using this method to applicable specifications, results shall be rounded in accordance with the rounding off methods of Practice E29.  
1.5 Review the current appropriate Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety precautions.  
1.6 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. Specific hazards statements are given in Section 7.  
1.7 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.

SIGNIFICANCE AND USE
5.1 Peroxy esters are widely used as chemical intermediates, catalysts, and initiators. This test method provides a procedure for assaying peroxy esters to determine if they are suitable for their intended use.
SCOPE
1.1 This test method covers the assay of organic peroxides of the peroxy ester type.  
Note 1: Other test methods for the assay of organic peroxides are given in Test Methods E298, E475, and E755.  
1.2 Review the current safety data sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety precautions.  
1.3 The values stated in SI units are to be regarded as the standard. No other units of measurement are included in this test method.  
1.4 In determining the conformance of the test results using this method to applicable specifications, results shall be rounded off in accordance with the rounding-off method of Practice E29.  
1.5 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. Specific hazards statements are given in Section 9.  
1.6 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.

SIGNIFICANCE AND USE
5.1 Hydroxyl is an important functional group and knowledge of its content is required in many intermediate and end use applications. This test method is for the determination of primary and secondary hydroxyl groups and can be used for the assay of compounds containing them.  
5.2 This test method has the following advantages over other hydroxyl number methods: It is rapid (10 min), pyridine-free, ambient temperature, small sample size, applicable to extremely low hydroxyl numbers (
SCOPE
1.1 This test method covers the determination of hydroxyl groups attached to primary and secondary carbon atoms in aliphatic and cyclic compounds and phenols from 0.5 to 367 hydroxyl number. It is not suitable for determination of hydroxyl groups attached to tertiary carbon atoms. This test method is applicable to polyacetals, temperature sensitive materials, high solids polymer polyols, and rigid polyols. Other available test methods listed in Note 1 are not suitable for many of the sample types listed above.  
1.1.1 This test method is currently recommended for neutral refined products. Successful application has been made, however, to some in-process samples that contain an excess of acidic species. Proper validation must be performed, of course, to show that the acidic species either does not interfere, or that the acidic species interference has been obviated.
Note 1: Other methods for determination of hydroxyl groups are given in Test Methods D817, D871, D4252, D4273, D4274, E222, E326, and E335.  
1.2 The Limit of Detection (LOD) is 0.18 units and the Limit of Quantitation (LOQ) is 0.59 units. Unit = hydroxyl number (OH#).
Note 2: LOD and LOQ were calculated using Standard deviations from 14.1.2.1.  
1.3 Review the current appropriate Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety precautions.  
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.5 The following applies for the purposes of determining the conformance of the test results using this test method to applicable specifications. Results shall be rounded off in accordance with the rounding-off method of Practice E29.  
1.6 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. For specific hazards see Section 9.  
1.7 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.

SIGNIFICANCE AND USE
3.1 Caustic soda and caustic potash are used in a large number of manufacturing processes. The chemicals are available in several grades depending on their intended use. The test methods listed in 1.2 provide procedures for analyzing caustic soda and caustic potash to determine if they are suitable for their intended use.
SCOPE
1.1 These test methods cover only the analyses usually required on the following commercial products:  
1.1.1 Caustic soda (sodium hydroxide), 50 and 73 % liquors; anhydrous (solid, flake, ground, or powdered), and  
1.1.2 Caustic potash (potassium hydroxide), 45 % liquor; anhydrous (solid, flake, ground, or powdered).  
1.2 The analytical procedures appear in the following order:    
Alkalinity (Total), Titrimetric (for 50 to 100 %
NaOH and 45 to 100 % KOH)  
3 to 4  
Carbonate, Gas-Volumetric (0.001 g CO2, min)  
4 to 7  
Carbonate, Gravimetric (0.001 g CO2, min)  
7 to 10  
Chloride, Titrimetric, (0.001 g Cl−, min)  
10 to 11  
Chloride, Potentiometric Titration (0.3 to 1.2 %)  
11 to 12  
Chloride, Ion Selective Electrode (0.6 to 120 μg/g)  
12 to 13  
Iron, Photometric (0.005 mg Fe, min)  
13 to 15  
Sulfate, Gravimetric, (0.002 g SO3, min)  
15 to 16  
Keywords  
16  
1.3 Units—The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard with the exception of inch-pound units for apparatus descriptions.  
1.4 In determining the conformance of the test results using this method to applicable specifications, results shall be rounded off in accordance with the rounding-off method of Practice E29.  
1.5 Review the current Safety Data Sheet (SDS) for detailed information concerning toxicity, first-aid procedures, handling, and safety precautions.  
1.6 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. Specific hazard statements are given in Section 6.  
1.7 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.

SIGNIFICANCE AND USE
4.1 Dilute solutions of peroxides in various organic solvents frequently are used as catalysts or reaction initiators. Peroxides also can be formed through autoxidation in certain classes of compounds including ethers, acetals, dienes, and alkylaromatic hydrocarbons and present a potential safety hazard. This test method provides a procedure for determining the peroxide or active oxygen level.
SCOPE
1.1 This test method2,3 covers organic solvents containing active oxygen in the range from 5 to 80 μg/g (ppm) or higher. By using a special reaction-absorption cell, the test method can be extended to cover the range from 0 to 5 ppm. The test method can be used to determine numerous peroxide classes of varying reactivity such as hydroperoxides, diacyl peroxides, diaroyl peroxides, peresters, and ketone peroxides. The stable di-tert-alkyl peroxides do not react under the conditions of analysis.  
1.2 Solvents that can be analyzed successfully include saturated and aromatic hydrocarbons, alcohols, ethers, ketones, and esters. In addition, the test method is applicable to olefinic solvents and to certain compounds that contain α, β, and conjugated unsaturation. Solid samples that are soluble in the acetic acid-chloroform solvent also can be analyzed.  
1.3 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid practices, and safety precautions.  
1.4 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.  
1.5 This standard does not purport to address the safety concerns, if any, associated with its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.  
1.6 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.

SIGNIFICANCE AND USE
3.1 Organic peroxides are widely used as chemical intermediates, catalysts, and initiators. These test methods provide procedures for assaying organic peroxides to determine if they are suitable for their intended use.
SCOPE
1.1 These test methods cover the assay of organic peroxides. Two procedures are given, depending upon the ease of reduction:  
1.1.1 Sodium Iodide, Room Temperature Test Method, for organic peroxides easy to reduce, and  
1.1.2 Sodium Iodide, 60°C Test Method, for organic peroxides that are moderately stable.  
1.2 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first-aid procedures, and safety precautions.  
1.3 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.  
1.4 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 health practices and determine the applicability of regulatory limitations prior to use.  
1.5 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.

SIGNIFICANCE AND USE
3.1 Soda ash is used in a number of manufacturing processes. The procedures listed in 1.2 are suitable for specification acceptance and manufacturing control of commercial soda ash.
SCOPE
1.1 These test methods cover the analyses usually required on commercial soda ash (sodium carbonate).  
1.2 The analytical procedures appear in the following sections:    
Sections  
Total Alkalinity, Titrimetric  
8 – 15  
Sodium Bicarbonate, Titrimetric  
17 – 24  
Loss on Heating, Gravimetric  
26 – 32  
Moisture, Calculation  
34 – 38  
Sodium Chloride, Titrimetric  
40 – 46  
Sodium Sulfate, Gravimetric  
48 – 54  
Iron, Photometric  
56 – 64  
Sieve Analysis  
66 – 72  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 In determining the conformance of the test results using this method to applicable specifications, results shall be rounded off in accordance with the rounding-off method of Practice E29.  
1.5 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, handling and safety precautions.  
1.6 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 health practices and determine the applicability of regulatory limitations prior to use. Specific hazards statements are given in Section 6.  
1.7 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.

SIGNIFICANCE AND USE
4.1 Anion impurities in caustic soda and caustic potash are monitored by manufacturers and users for quality control of the products. Anions of primary interest are chloride, chlorate, and sulfate. This test method has determined precision estimates only for these three impurities.
SCOPE
1.1 This test method covers the determination of anionic impurities in 50 % caustic soda (sodium hydroxide) and 50 % caustic potash (potassium hydroxide) solutions using ion chromatography (IC). Anions that can be determined at concentrations of approximately 0.1 to 1000 ug/g (ppm) include: bromide, chlorate, chloride, fluoride, nitrate, phosphate, and sulfate.  
1.2 By varying the sample size, this test method can be used for anhydrous caustic soda and caustic potash products, as well as other concentrations of liquid products.  
1.3 This test method is not intended to be used to quantify chloride in caustic soda where the sodium chloride concentration is approximately 1 %. For the most accurate determinations, it is recommended that high concentrations of chloride be analyzed using a potentiometric titration procedure, such as the one described in Test Methods E291.  
1.4 The values stated in SI units are to be regarded as standard. The values given in parentheses are for information only.  
1.5 Review the current appropriate Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety precautions.  
1.6 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 health practices and determine the applicability of regulatory limitations prior to use. Specific hazards statements are given in Section 8.

SIGNIFICANCE AND USE
5.1 Di-tert-butyl peroxide is widely used as a catalyst and reaction initiator. Knowledge of the peroxide content is important in such applications. This test method provides a procedure for determining the active peroxide content of commercial di-tert-butyl peroxide.
SCOPE
1.1 This test method covers the assay of di-tert-butyl peroxide using gas chromatography. It is applicable to commercial di-tert-butyl peroxide which may contain small amounts of isobutylene, tert-butanol, tert-butyl hydroperoxide, triisobutylenes, and water as impurities.  
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 health practices and determine the applicability of regulatory limitations prior to use. Specific hazards statements are given in Section 9.

SIGNIFICANCE AND USE
4.1 Hydroxyl is an important functional group, and knowledge of its content is required in many intermediate and end use applications. The test methods described herein are for the determination of primary and secondary hydroxyl groups and can be used for the assay of compounds containing them.
SCOPE
1.1 These test methods cover the determination of hydroxyl groups attached to primary and secondary carbon atoms in aliphatic and alicyclic compounds and phenols.  
1.2 Three test methods are given as follows:    
Sections  
Test Method A (Pressure Bottle Method)  
8 – 14    
Test Method B (Reflux Method)  
16 – 22    
Test Method C (Perchloric Acid Catalyzed Method)  
24 – 30  
1.2.1 Test Method A is recommended for general use. Test Method B is included to give a standard procedure for the method that has been used widely. Test Method C is recommended when the results are required in a minimum period of time or where ambient temperature for the reaction is desired.  
1.2.2 The results obtained using Test Methods A and B will be essentially the same, but the results obtained using Test Method C will be higher (up to approximately 4 % relative) than those obtained using the other two methods.  
1.2.3 Statements on precision are included with each test method. The precision of Test Methods A and C is consistent over a wide range of hydroxyl content (tested over hydroxyl number range of 250 to 1600), whereas Test Method B is less precise at the higher hydroxyl content level than it is at the lower hydroxyl content level. In general, Test Method A is approximately two-fold as precise as Test Method C. Test Method B has approximately the same precision as Test Method C at the lower hydroxyl content level but poorer precision at the higher hydroxyl content level.  
1.2.4 The interferences are essentially the same for the three methods. Some compounds can be analyzed using Test Methods A or B but not using Test Method C because of interfering reactions of the strong acid catalyst with the compound being analyzed or the acetate product formed in the determination. However, because of its increased reactivity, Test Method C is applicable for determination of some compounds, particularly sterically hindered secondary alcohols, which react too slowly or not at all in Test Methods A and B.
Note 1: Other methods for determination of hydroxyl groups are given in Test Methods D1957, D2195, E326, E335, and E567.  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 Review the current appropriate Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety precautions.  
1.5 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 health practices and determine the applicability of regulatory limitations prior to use. Specific hazards statements are given in Section 7.  
1.6 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.

SIGNIFICANCE AND USE
5.1 Peroxy esters are widely used as chemical intermediates, catalysts, and initiators. This test method provides a procedure for assaying peroxy esters to determine if they are suitable for their intended use.
SCOPE
1.1 This test method covers the assay of organic peroxides of the peroxy ester type.  
Note 1: Other test methods for the assay of organic peroxides are given in Test Methods E298, E475, and E755.  
1.2 Review the current safety data sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety precautions.  
1.3 The values stated in SI units are to be regarded as the standard. No other units of measurement are included in this test method.  
1.4 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 health practices and determine the applicability of regulatory limitations prior to use. Specific hazards statements are given in Section 9.  
1.5 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.

SIGNIFICANCE AND USE
5.1 Hydroxyl is an important functional group and knowledge of its content is required in many intermediate and end use applications. This test method is for the determination of primary and secondary hydroxyl groups and can be used for the assay of compounds containing them.  
5.2 This test method has the following advantages over other hydroxyl number methods: It is rapid (10 min), pyridine-free, ambient temperature, small sample size, applicable to extremely low hydroxyl numbers (
SCOPE
1.1 This test method covers the determination of hydroxyl groups attached to primary and secondary carbon atoms in aliphatic and cyclic compounds and phenols. It is not suitable for determination of hydroxyl groups attached to tertiary carbon atoms. This test method is applicable to polyacetals, temperature sensitive materials, high solids polymer polyols, and rigid polyols. Other available test methods listed in Note 1 are not suitable for many of the sample types listed above.  
1.1.1 This test method is currently recommended for neutral refined products. Successful application has been made, however, to some in-process samples that contain an excess of acidic species. Proper validation must be performed, of course, to show that the acidic species either does not interfere, or that the acidic species interference has been obviated.
Note 1: Other methods for determination of hydroxyl groups are given in Test Methods D817, D871, D1957, D2195, D4252, D4273, D4274, E222, E326, and E335.  
1.2 Review the current appropriate Safety Data Sheets (SDS) for detailed information concerning toxicity, first aid procedures, and safety precautions.  
1.3 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.4 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 health practices and determine the applicability of regulatory limitations prior to use. For specific hazards see Section 9.

SIGNIFICANCE AND USE
4.1 Mercury is a toxic material and is also deleterious if present in caustic soda and caustic potash used in certain manufacturing processes. It must therefore be controlled as a possible pollutant. These test methods provide a procedure for measuring mercury in liquid and solid caustic soda and caustic potash.
SCOPE
1.1 These test methods cover the routine determination of mercury in caustic soda and caustic potash liquors and anhydrous caustic soda in the solid, flake, ground, and bead form by the flameless atomic absorption method.  
1.2 Two test methods are described as follows: Test Method A employs a direct analysis of the sample using an alkaline reducing agent with a lower limit of detection of 0.1 ppb (ng/g). Test Method A was developed using caustic soda and caustic potash. Test Method B requires a preliminary neutralization of the sample followed by a permanganate oxidation before it can be analyzed by an acidic reducing agent with a lower limit of detection of this test method of 0.01 ppm (μg/g). Test Method B was developed using caustic soda.  
1.3 Review the current Safety Data Sheets (SDS) for detailed information concerning toxicity, first-aid procedures, and safety precautions.  
1.4 The values stated in SI units are to be regarded as standard. No other units of measurement are included in this standard.  
1.5 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 health practices and determine the applicability of regulatory limitations prior to use. Specific hazards statements are given in Sections 7 and 18.  
1.6 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.
WITHDRAWN RATIONALE
These test methods cover the routine determination of mercury in caustic soda and caustic potash liquors and anhydrous caustic soda in the solid, flake, ground, and bead form by the flameless atomic absorption method. Formerly under the jurisdiction of Committee D16 on Aromatic, Industrial, Specialty and Related Chemicals, this test method was withdrawn in May 2023. This standard is being withdrawn without replacement due to its limited use by industry.