Thermodynamics of Polymerization. I
Abstract
I. THE CHILING TEMPERATURE CONCEPT A. Thermodynamic Approach The Gibbs free energy of a system at temperature T is defined as were H is the enthalpy and S the entropy of the system. The free energy change for any polymerization will be, therefore, When the polymer has a lower free energy than the initial monomer, a polymerization can occur spontaneously, and the sign of ΔG is negative. A positive sign for ΔG signifies, therefore, that the polymerization is not spontaneous. When the system is in equilibrium at a certain critical temperature, there is no tendency for polymerization, and, hence, ΔG = 0 [1–3]. This temperature is known as the ceiling temperature. These three possible conditions for free energy change of polymerization may be summarized as follows: At the ceiling temperature, Tc, ΔG is zero, so that where ΔHp and ΔSp are the enthalpy and entropy changes per monomer unit.
Integrity signals
Registry
Cites
Statistics
Claims the paper makes
Claims other papers make about this one
Each is checked against this paper’s own text: does it say what the citing paper says it does?
Gains in rotational and vibrational degrees of freedom can lead to positive changes in ΔS_p° but are only rarely large enough to fully offset the large decrease in translational entropy that usually accompanies polymerization.
“Gains in rotational and vibrational degrees of freedom can lead to positive changes in Δ S p ° but are only rarely large enough to fully o ff set the large decrease in translational entropy that usually accompanies polymerization. 71,72”
From Aliphatic Polyester Block Polymer Design (2016) · cites this paper as [72]
No citation lists for this paper
No citation lists for this paper yet — checked again daily.
References 28 · Cited by 72
Research works printed but not linked: 42
- 10.1038/162705a0 · DOI
- 10.1039/tf9504600331 · DOI
- 10.1039/qr9581200061 · DOI
- Ivin K. J. , inPolymer Handbook( Brandrup J. Immergut E. M. , eds.), Wiley-Interscience , New York , 1966 , 11 – 363 .
- Joshi R. M. Zwolinski B. J. , inVinyl Polymerization( Ham G. E. , ed.), 1 , Dekker , New York , 1967 , p. 494 .
- Temperley H. N. V., 1956, J. Res. Natl. Bur. Std., 56, 55, 10.6028/jres.056.008 · DOI
- 10.1016/0032-3861(62)90087-3 · DOI
- 10.1002/macp.1962.020510110 · DOI
- 10.1016/0032-3861(62)90087-3 · DOI
- Warrield R. W., 1967, J. Polymer Sci., 2, 791
- Furukawa G. T., 1956, J. Res. Natl. Bur. Std., 56, 285, 10.6028/jres.056.036 · DOI
- Dainton F. S., 1967, Polymer, 3, 297
- Bekkedahl N., 1935, J. Res. Natl. Bur. Std., 15, 503, 10.6028/jres.015.034 · DOI
- Warfield R. W., 1962, Kolloid-Z., 185, 63, 10.1007/BF01882352 · DOI
- Warfield R. W., 1966, J. Polymer Sci., 4, 532
- Melia T. P., 1962, Polymer, 3, 317
- 10.1016/0032-3861(62)90087-3 · DOI
- 10.1002/jctb.5010170104 · DOI
- Furukawa G. T., 1952, J. Res. Natl. Bur. Std., 49, 273, 10.6028/jres.049.029 · DOI
- 10.1016/0032-3861(62)90087-3 · DOI
- 10.1016/0032-3861(62)90087-3 · DOI
- 10.1016/0032-3861(62)90087-3 · DOI
- 10.1002/macp.1968.021120109 · DOI
- 10.1002/macp.1967.021090109 · DOI
- 10.1002/macp.1968.021160112 · DOI
- 10.1002/pol.1961.1205516208 · DOI
- Warfield R. W., 1963, J. Polymer Sci., 1, 1701
- 10.1016/0032-3861(68)90018-9 · DOI
- 10.1039/tf9605601784 · DOI
- 10.1002/jctb.5010141101 · DOI
- 10.1063/1.1746970 · DOI
- 10.1063/1.1750058 · DOI
- 10.1039/tf9474300210 · DOI
- Joshi R. M., 1967, Vinyl Polymerization, 1
- 10.1021/ma60001a005 · DOI
- Parks G. S., 1963, J. Polymer Sci., 1, 1979
- 10.1016/0032-3861(66)90022-X · DOI
- 10.1039/tf9555101267 · DOI
- 10.1039/tf9534900441 · DOI
- Flory P. J., 1953, Principles of Polymer Chemistry
- 10.1002/macp.1962.020520110 · DOI
- 10.1016/0032-3861(65)90057-1 · DOI
- Authors
- Sawada, H.
- Corresponding author
- Sawada, Hideo
- ORCID
- Sawada, Hideo
- Venue
- Journal of Macromolecular Science, Part C: Polymer Reviews
- Publisher
- Informa UK Limited
- Published
- 1969-01
- Volume
- 3
- Issue
- 2
- Pages
- 313-338
- ISSN
- 0736-6574 (ISSN-L)
- 1532-1797
- 1520-5746
- OpenAlex
- W4245819950
- Cited by
- 72
- References
- 28
- Citations by year
- 2026: 1 · 2025: 4 · 2024: 5 · 2022: 2 · 2021: 4 · 2020: 4 · 2019: 2 · 2018: 1 · 2016: 2 · 2015: 5 · 2013: 3 · 2012: 1
- FWCI
- 1.95
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of macromolecular science. Part C, Reviews in macromolecular chemistry and physics/Journal of macromolecular science. Reviews in macromolecular chemistry and physics (publishedVersion)
- Topics
- Physical Sciences › Chemistry › Organic Chemistry › Advanced Polymer Synthesis and Characterization
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Phase Equilibria and Thermodynamics
- Physical Sciences › Chemistry › Organic Chemistry › Chemical Thermodynamics and Molecular Structure
- Keywords
- polymerization thermodynamics, Gibbs free energy, ceiling temperature, enthalpy change, entropy change, polymerization kinetics
About these checks
Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.
Statistics and arithmetic are recomputed, not judged.
Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.
What counts as a claim ›How we measure confidence ›How we check this ›
Are you an author, or do you see a problem with this page? Request a review
