Standard Test Methods for Hydroxyl Groups Using Acetic Anhydride Acetylation

SIGNIFICANCE AND USE
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) 15-21  Test Method C (Perchloric Acid Catalyzed Method) 22-28  
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.
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 Material Safety Data Sheets (MSDS) 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.  
Note 1—Other methods for determination of hydroxyl groups are given in Test Methods D1957, D2195, E326, E335, and .

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Standards Content (Sample)

NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.
Contact ASTM International (www.astm.org) for the latest information
Designation: E222 − 10
Standard Test Methods for
1
Hydroxyl Groups Using Acetic Anhydride Acetylation
This standard is issued under the fixed designation E222; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1. Scope* 1.3 The values stated in SI units are to be regarded as
standard. No other units of measurement are included in this
1.1 These test methods cover the determination of hydroxyl
standard.
groups attached to primary and secondary carbon atoms in
aliphatic and alicyclic compounds and phenols. 1.4 Review the current appropriate Material Safety Data
Sheets (MSDS) for detailed information concerning toxicity,
1.2 Three test methods are given as follows:
first aid procedures, and safety precautions.
Sections
Test Method A (Pressure Bottle Method) 8–14 1.5 This standard does not purport to address all of the
Test Method B (Reflux Method) 15–21
safety concerns, if any, associated with its use. It is the
Test Method C (Perchloric Acid Catalyzed Method) 22–28
responsibility of the user of this standard to establish appro-
1.2.1 Test Method A is recommended for general use. Test
priate safety and health practices and determine the applica-
Method B is included to give a standard procedure for the
bility of regulatory limitations prior to use. Specific hazards
method that has been used widely. Test Method C is recom-
statements are given in Section 7.
mended when the results are required in a minimum period of
NOTE1—Othermethodsfordeterminationofhydroxylgroupsaregiven
time or where ambient temperature for the reaction is desired.
in Test Methods D1957, D2195, E326, E335, and E567.
1.2.2 The results obtained using Test MethodsAand B will
be essentially the same, but the results obtained using Test
2. Referenced Documents
Method C will be higher (up to approximately 4% relative)
2
2.1 ASTM Standards:
than those obtained using the other two methods.
D1193Specification for Reagent Water
1.2.3 Statements on precision are included with each test
D1957Test Method for Hydroxyl Value of Fatty Oils and
method. The precision of Test Methods A and C is consistent
3
Acids (Withdrawn 2007)
over a wide range of hydroxyl content (tested over hydroxyl
3
D2195Test Methods for Pentaerythritol (Withdrawn 2011)
number range of 250 to 1600), whereas Test Method B is less
E180Practice for Determining the Precision of ASTM
precise at the higher hydroxyl content level than it is at the
Methods for Analysis and Testing of Industrial and Spe-
lower hydroxyl content level. In general, Test Method A is
3
cialty Chemicals (Withdrawn 2009)
approximately two-fold as precise as Test Method C. Test
E200Practice for Preparation, Standardization, and Storage
Method B has approximately the same precision as Test
of Standard and Reagent Solutions for ChemicalAnalysis
Method C at the lower hydroxyl content level but poorer
E203Test Method for Water Using Volumetric Karl Fischer
precision at the higher hydroxyl content level.
Titration
1.2.4 Theinterferencesareessentiallythesameforthethree
E326Test Method for Hydroxyl Groups by Phthalic Anhy-
methods. Some compounds can be analyzed using Test Meth-
3
dride Esterification (Withdrawn 2001)
odsAor B but not using Test Method C because of interfering
E335Test Method for Hydroxyl Groups by Pyromellitic
reactions of the strong acid catalyst with the compound being
3
Dianhydride Esterification (Withdrawn 2002)
analyzed or the acetate product formed in the determination.
E567Test Method for Tertiary Hydroxyl Groups with Hy-
However, because of its increased reactivity, Test Method C is
3
drogen Bromide (Withdrawn 1996)
applicable for determination of some compounds, particularly
sterically hindered secondary alcohols, which react too slowly
3. Terminology
or not at all in Test Methods A and B.
3.1 Definitions:
1 2
These test methods are under the jurisdiction of ASTM Committee D16 on For referenced ASTM standards, visit the ASTM website, www.astm.org, or
Aromatic Hydrocarbons and Related Chemicals and are the direct responsibility of contact ASTM Customer Service at service@astm.org. For Annual Book of ASTM
Subcommittee D16.15 on Industrial and Specialty General Standards. Standards volume information, refer to the standard’s Document Summary page on
Current edition approved March 1, 2010. Published April 2010. Originally the ASTM website.
ε1 3
approved in 1963. Last previous edition approved in 2005 as E222–00 (2005) . The last approved version of this historical standard is referenced on
DOI: 10.1520/E0222-10. www.astm.org.
*A Summary of Changes section appears at the end of this standard
Copyright © AS
...

This document is not anASTM standard and is intended only to provide the user of anASTM 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.
´1
Designation:E222–00(Reapproved2005) Designation:E222–10
Standard Test Methods for
1
Hydroxyl Groups Using Acetic Anhydride Acetylation
This standard is issued under the fixed designation E222; the number immediately following the designation indicates the year of
original adoption or, in the case of revision, the year of last revision.Anumber in parentheses indicates the year of last reapproval.A
superscript epsilon (´) indicates an editorial change since the last revision or reapproval.
1
´ NOTE—Editorial changes were made in March 2005.
1. Scope*
1.1 Thesetestmethodscoverthedeterminationofhydroxylgroupsattachedtoprimaryandsecondarycarbonatomsinaliphatic
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) 15-21
Test Method C (Perchloric Acid Catalyzed Method) 22-28
1.2.1 Test MethodAis 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 usingTest MethodsAand B will be essentially the same, but the results obtained usingTest 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 MethodsAand C is consistent over a
wide range of hydroxyl content (tested over hydroxyl number range of 250 to 1600), whereasTest Method B is less precise at the
higher hydroxyl content level than it is at the lower hydroxyl content level. In general, Test MethodAis approximately two-fold
aspreciseasTestMethodC.TestMethodBhasapproximatelythesameprecisionasTestMethodCatthelowerhydroxylcontent
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
Aor B but not usingTest 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 inTest
Methods A and B.
1.3 The values stated in SI units are to be regarded as the standard.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 Material Safety Data Sheets (MSDS) 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.
NOTE 1—Other methods for determination of hydroxyl groups are given in Test Methods D1957, D2195, E326, E335, and E567.
2. Referenced Documents
2
2.1 ASTM Standards:
D1193 Specification for Reagent Water
D1957 Test Method for Hydroxyl Value of Fatty Oils and Acids
1
These test methods are under the jurisdiction ofASTM Committee E15 on Industrial and Specialty Chemicals and are the direct responsibility of Subcommittee E15.01
on General Standards.
Current edition approved March 1, 2005. Published April 2005. Originally approved in 1963. Last previous edition approved in 2000 as E222–00. DOI:
10.1520/E0222-00R05E01.
´1
Current edition approved March 1, 2010. Published March 2010. Originally approved in 1963. Last previous edition approved in 2005 as E222–00(05) . DOI:
10.1520/E0222-10.
2
ForreferencedASTMstandards,visittheASTMwebsite,www.astm.org,orcontactASTMCustomerServiceatservice@astm.org.For Annual Book of ASTM Standards
volume information, refer to the standard’s Document Summary page on the ASTM website.
*A Summary of Changes section appears at the end of this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959, United States.
1

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E222–10
D2195 Test Methods for Pentaerythritol
E180 PracticeforDeterminingthePrecisionofASTMMethodsforAnalysisandTestingof
...

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