Infrared laser heating for studies of cellulose degradation

John P. Jackson; Eugene Arthurs; Larry A. Schwalbe; Ronald M. Sega; David E. Windisch; William H. Long; Eddy A. Stappaerts

doi:10.1364/AO.27.003937

Applied Optics
Vol. 27,
Issue 18,
pp. 3937-3943
(1988)
•https://doi.org/10.1364/AO.27.003937

Infrared laser heating for studies of cellulose degradation

John P. Jackson, Eugene Arthurs, Larry A. Schwalbe, Ronald M. Sega, David E. Windisch, William H. Long, and Eddy A. Stappaerts

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John P. Jackson, Eugene Arthurs, Larry A. Schwalbe, Ronald M. Sega, David E. Windisch, William H. Long, and Eddy A. Stappaerts, "Infrared laser heating for studies of cellulose degradation," Appl. Opt. 27, 3937-3943 (1988)

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Abstract

We describe a new technique for studying thermally induced chemical transformations in cellulose. The apparatus consists of a carbon dioxide laser for heating, an IR thermometer, and an optical reflectance spectrometer for tracking the progressive discoloration of the sample. To illustrate the technique, we present measurements from a single piece of sample linen along five isotherms in the 200–290°C range. We derive an algebraic expression for the reflectivity of the sample as a function of the areal concentrations of the chromophoric states produced at temperature. The results are then explained in terms of first-order chemical rate theory and a four-step model. From the measurements we derive the activation energies, Arrhenius constants, and reflectivities of the chromophoric states.

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T	K₀₁	K₁₂	K₂₃	K₃₄	r₁	r₂	r₃	r₄	σ
135 (oven)	2.4 × 10⁻³	1.2 × 10⁻⁵	—	—	0.96	0.72	—	—	6.9 × 10⁻³
203 (first pair)	6.3 × 10⁻²	1.5 × 10⁻³	—	—	0.96	0.73	—	—	2.5 × 10⁻³
203 (second pair)	—	2.0 × 10⁻³	2.0 × 10⁻⁴	—	—	0.80	0.33	—	5.1 × 10⁻³
224	—	1.2 × 10⁻²	1.6 × 10⁻³	—	—	0.82	0.34	—	2.7 × 10⁻³
247	—	3.9 × 10⁻²	4.8 × 10⁻³	—	—	0.71	0.33	—	3.3 × 10⁻³
270	—	—	6.5 × 10⁻²	7.7 × 10⁻³	—	—	0.35	0.05	3.4 × 10⁻³
292	—	—	1.3 × 10⁻¹	2.0 × 10⁻³	—	—	0.28	0.04	4.0 × 10⁻³

					(0.96)	(0.76 ± 0.05)	(0.33 ± 0.03)	(0.045 ± 0.007)

Activation energy (eV)	Arrhenius constant (s⁻¹)
E₀₁ = 0.81	A₀₁ = 2.16 × 10⁷
E₁₂ = 1.30 ± 0.05	A₁₂ = 1.25 ± 1.67 × 10¹¹
E₂₃ = 1.73 ± 0.14	A₂₃ = 4.26 ± 13.4 × 10¹⁴
E₃₄ = 1.16	A₃₄ = 4.00 × 10⁸

T	K₀₁	K₁₂	K₂₃	K₃₄	r₁	r₂	r₃	r₄	σ
135 (oven)	2.4 × 10⁻³	1.2 × 10⁻⁵	—	—	0.96	0.72	—	—	6.9 × 10⁻³
203 (first pair)	6.3 × 10⁻²	1.5 × 10⁻³	—	—	0.96	0.73	—	—	2.5 × 10⁻³
203 (second pair)	—	2.0 × 10⁻³	2.0 × 10⁻⁴	—	—	0.80	0.33	—	5.1 × 10⁻³
224	—	1.2 × 10⁻²	1.6 × 10⁻³	—	—	0.82	0.34	—	2.7 × 10⁻³
247	—	3.9 × 10⁻²	4.8 × 10⁻³	—	—	0.71	0.33	—	3.3 × 10⁻³
270	—	—	6.5 × 10⁻²	7.7 × 10⁻³	—	—	0.35	0.05	3.4 × 10⁻³
292	—	—	1.3 × 10⁻¹	2.0 × 10⁻³	—	—	0.28	0.04	4.0 × 10⁻³

					(0.96)	(0.76 ± 0.05)	(0.33 ± 0.03)	(0.045 ± 0.007)

Activation energy (eV)	Arrhenius constant (s⁻¹)
E₀₁ = 0.81	A₀₁ = 2.16 × 10⁷
E₁₂ = 1.30 ± 0.05	A₁₂ = 1.25 ± 1.67 × 10¹¹
E₂₃ = 1.73 ± 0.14	A₂₃ = 4.26 ± 13.4 × 10¹⁴
E₃₄ = 1.16	A₃₄ = 4.00 × 10⁸

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Equations (16)

Applied Optics