ASTM E2781-11

Standard Practice for Evaluation of Methods for Determination of Kinetic Parameters by Thermal Analysis

SIGNIFICANCE AND USE
The kinetic parameters provided in this standard may be used to evaluate the performance of a standard, apparatus, techniques or software for the determination parameters (such as Test Methods E698, E1641, E2041, or E2070) using thermal analysis techniques such as differential scanning calorimetry, and accelerating rate calorimetry (Guide E1981). The results obtained by these approaches may be compared to the values provided by this practice.
Note 4—Not all reference materials are suitable for each measurement technique.
SCOPE
1.1 It is the purpose of this Practice to provide kinetic parameters for reference materials used for evaluation of thermal analysis methods, apparatus and software where enthalpy and temperature are measured. This Practice addresses both exothermic and endothermic, nth order and autocatalytic reactions.  
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 There is no International Organization for Standardization (ISO) equivalent to 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.

General Information

• Status: Historical
• Publication Date: 28-Feb-2011
• ICS: 17.200.10 - Heat. Calorimetry
• Technical Committee: E37 - Thermal Measurements
• Drafting Committee: E37.02 - Reference Materials

Relations

• Replaced By: ASTM E2781-16 - Standard Practice for Evaluation of Methods for Determination of Kinetic Parameters by Calorimetry and Differential Scanning Calorimetry
• Effective Date: 01-Nov-2016
• Referred By: ASTM E698-23 - Standard Test Method for Kinetic Parameters for Thermally Unstable Materials Using Differential Scanning Calorimetry and the Flynn/Wall/Ozawa Method
• Effective Date: 01-Mar-2011
• Referred By: ASTM E2041-23 - Standard Test Method for Estimating Kinetic Parameters by Differential Scanning Calorimeter Using the Borchardt and Daniels Method
• Effective Date: 01-Mar-2011

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NOTICE: This standard has either been superseded and replaced by a new version or withdrawn.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: E2781 − 11
StandardPractice for
Evaluation of Methods for Determination of Kinetic
1
Parameters by Thermal Analysis
This standard is issued under the fixed designation E2781; 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 and Daniels Method
E2070Test Method for Kinetic Parameters by Differential
1.1 It is the purpose of this practice to provide kinetic
Scanning Calorimetry Using Isothermal Methods
parameters for reference materials used for evaluation of
thermal analysis methods, apparatus and software where en-
3. Terminology
thalpy and temperature are measured. This practice addresses
3.1 Definitions—Specific technical terms used in this prac-
both exothermic and endothermic, nth order and autocatalytic
tice are defined in Terminologies E473 and E1142, including
reactions.
differential scanning calorimetry.
1.2 The values stated in SI units are to be regarded as
4. Summary of Practice
standard. No other units of measurement are included in this
standard.
4.1 Kinetics is the study of the relationship of the extent of
a chemical reaction to the independent parameters of time and
1.3 There is no International Organization for Standardiza-
temperature. This relationship is often described using the
tion (ISO) equivalent to this standard.
Arrhenius expression where:
1.4 This standard does not purport to address all of the
dα/dt 5Zf α exp 2E/RT (1)
safety concerns, if any, associated with its use. It is the ~ ! ~ !
responsibility of the user of this standard to establish appro-
where:
priate safety and health practices and determine the applica-
α = fraction left to react,
bility of regulatory limitations prior to use.
f(α) = some function of (α),
E = activation energy (J/mol),
2. Referenced Documents
–1 –1
R = gas constant (=8.314J mol K ),
2
2.1 ASTM Standards:
T = absolute temperature (K), and
E473Terminology Relating to Thermal Analysis and Rhe- Z = pre-exponential factor (1/sec).
ology
4.2 For many reactions of interest the description of the
E698Test Method for Arrhenius Kinetic Constants for
function of amount left to react is of the form:
Thermally Unstable Materials Using Differential Scan-
m n
f~α! 5α ~1 2α! (2)
ning Calorimetry and the Flynn/Wall/Ozawa Method
E1142Terminology Relating to Thermophysical Properties
where m and n are the overall reaction orders. This form of
E1641TestMethodforDecompositionKineticsbyThermo-
the concentration dependence is known as the auto-catalytic
3
gravimetry Using the Ozawa/Flynn/Wall Method
form or the Sestak-Berggren reaction (1). If the value of m
n
E1981Guide for Assessing Thermal Stability of Materials
equals 0, then f(α) reduces to the form of f(α)=(1–α)
by Methods of Accelerating Rate Calorimetry
commonly call nth order reaction.
E2041Test Method for Estimating Kinetic Parameters by
4.3 Eq 1 may be evaluated in either its exponential or
Differential Scanning Calorimeter Using the Borchardt
logarithmic form:
ln dα/dt 5 lnZ1ln f α 2 E/RT (3)
~ ! ~ ~ !!
1
This practice is under the jurisdiction of ASTM Committee E37 on Thermal
4.4 The study of kinetics involves the determination of
Measurements and is the direct responsibility of Subcommittee E37.02 on Standard
values of E, Z, m, and n for a given reaction.
Reference Materials.
Current edition approved March 1, 2011. Published April 2011. DOI: 10.1520/
NOTE1—Activationenergyandpre-exponentialfactorarenotindepen-
E2781-11.
dent parameters but are inter-related.
2
For referenced ASTM standards, visit the ASTM website, www.astm.org, or
contact ASTM Customer Service at [e-mail]. For Annual Book of ASTM
3
Standards volume information, refer to the standard’s Document Summary page on The boldface numbers in parentheses refer to a list of references at the end of
the ASTM website. this standard.
Copyright © ASTM International, 100 Barr Harbor Drive, PO Box C700, West Conshohocken, PA 19428-2959. United States
1

---------------------- Page: 1 ----------------------
E2781 − 11
NOTE 2—The descriptions provided in Eq 1-3 are only mathematical NOTE 4—Not all reference materials are suitable for each measurement
models. That is, they represent the fitting of mathematical equations to technique.
often “noisy” experimental data. In practice no such model will faithfully
describe the complete reaction(s) under all conditions for the materials
6. Hazards
described in this practice.
6.1 Thermally reactive materials evolve heat as part of the
4.5 Values for the kinetic parameter are typically in the
indicated reaction. Build up of this heat may lead to a
ranges indicated below:
dangerous over-pr
...