A critical evaluation of reaction calorimetry for the study of emulsion polymerization systems: thermodynamic and kinetic aspects

David J Lamb; Christopher Fellows; Bradley R Morrison; Robert G Gilbert

doi:10.1016/j.polymer.2004.11.026

A critical evaluation of reaction calorimetry for the study of emulsion polymerization systems: thermodynamic and kinetic aspects

David J Lamb
, Christopher Fellows
, Bradley R Morrison
, Robert G Gilbert

School of Science & Technology

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

Protocols were examined for the measurement of rates and enthalpies of polymerization (ΔHp) using reaction calorimetry. ΔHp was determined to be 70.2 kJ mol^-1 for a series of seeded styrene emulsion polymerizations under typical emulsion conditions, in good agreement with literature values. However, there was a significant deviation from this value for small-particle systems, which is ascribed to surface effects, i.e. environmental effects on ΔHp. Careful comparison between rate data obrained by calorimetry and by dilametry leads to recommended procedures for obtaining reliable and accurate rate data using the former technique.

Original language	English
Pages (from-to)	285-294
Journal	Polymer
Volume	46
Issue number	2
DOIs	https://doi.org/10.1016/j.polymer.2004.11.026
Publication status	Published - 2005

Keywords

Chemical Thermodynamics and Energetics
Polymerisation Mechanisms

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https://hdl.handle.net/1959.11/4583

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title = "A critical evaluation of reaction calorimetry for the study of emulsion polymerization systems: thermodynamic and kinetic aspects",

abstract = "Protocols were examined for the measurement of rates and enthalpies of polymerization (ΔHp) using reaction calorimetry. ΔHp was determined to be 70.2 kJ mol\textasciicircum{}-1 for a series of seeded styrene emulsion polymerizations under typical emulsion conditions, in good agreement with literature values. However, there was a significant deviation from this value for small-particle systems, which is ascribed to surface effects, i.e. environmental effects on ΔHp. Careful comparison between rate data obrained by calorimetry and by dilametry leads to recommended procedures for obtaining reliable and accurate rate data using the former technique.",

keywords = "Chemical Thermodynamics and Energetics, Polymerisation Mechanisms",

author = "Lamb, \{David J\} and Christopher Fellows and Morrison, \{Bradley R\} and Gilbert, \{Robert G\}",

year = "2005",

doi = "10.1016/j.polymer.2004.11.026",

language = "English",

volume = "46",

pages = "285--294",

journal = "Polymer",

issn = "0032-3861",

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TY - JOUR

T1 - A critical evaluation of reaction calorimetry for the study of emulsion polymerization systems

T2 - thermodynamic and kinetic aspects

AU - Lamb, David J

AU - Fellows, Christopher

AU - Morrison, Bradley R

AU - Gilbert, Robert G

PY - 2005

Y1 - 2005

N2 - Protocols were examined for the measurement of rates and enthalpies of polymerization (ΔHp) using reaction calorimetry. ΔHp was determined to be 70.2 kJ mol^-1 for a series of seeded styrene emulsion polymerizations under typical emulsion conditions, in good agreement with literature values. However, there was a significant deviation from this value for small-particle systems, which is ascribed to surface effects, i.e. environmental effects on ΔHp. Careful comparison between rate data obrained by calorimetry and by dilametry leads to recommended procedures for obtaining reliable and accurate rate data using the former technique.

AB - Protocols were examined for the measurement of rates and enthalpies of polymerization (ΔHp) using reaction calorimetry. ΔHp was determined to be 70.2 kJ mol^-1 for a series of seeded styrene emulsion polymerizations under typical emulsion conditions, in good agreement with literature values. However, there was a significant deviation from this value for small-particle systems, which is ascribed to surface effects, i.e. environmental effects on ΔHp. Careful comparison between rate data obrained by calorimetry and by dilametry leads to recommended procedures for obtaining reliable and accurate rate data using the former technique.

KW - Chemical Thermodynamics and Energetics

KW - Polymerisation Mechanisms

UR - http://trove.nla.gov.au/work/11237370

U2 - 10.1016/j.polymer.2004.11.026

DO - 10.1016/j.polymer.2004.11.026

M3 - Article

SN - 0032-3861

VL - 46

SP - 285

EP - 294

JO - Polymer

JF - Polymer

IS - 2

ER -

A critical evaluation of reaction calorimetry for the study of emulsion polymerization systems: thermodynamic and kinetic aspects

Abstract

Keywords

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