Polyethylene Glycols as Efficient Media for Decarboxylative Nitration of α,β-Unsaturated Aromatic Carboxylic Acids by Ceric Ammonium Nitrate in Acetonitrile Medium: A Kinetic and Mechanistic Study

Table 2

Activation parameters of cinnamic acid in different PEG media. Units of 𝑘^′′ = dm³ mol⁻¹ min⁻¹.

Type of PEG	PEG	𝑘^′′ at	Equation	𝑅^2	Δ𝐻^#	Δ𝐺^#	Δ𝑆^#
	% (V/V)	300 K			kJ/mol		J/K/mol
	0.5	0.01	𝑦 = −13.32𝑥 + 34.09	0.999	110	84.2	85.9
	1.0	0.02	𝑦 = −9.181𝑥 + 20.97	0.999	76.3	83.3	−23.2
PEG-200	2.0	0.03	𝑦 = −8.399𝑥 + 18.75	0.995	70.0	95.5	−41.7
	3.0	0.04	𝑦 = −8.625𝑥 + 19.84	0.998	91.8	81.8	−32.6
	4.0	0.08	𝑦 = −7.047𝑥 + 15.06	0.999	58.6	55.6	−72.3
	5.0	0.1	𝑦 = −8.112𝑥 + 19.01	0.995	67.5	39.7	39.5
	0.5	0.01	𝑦 = −22.79𝑥 + 64.43	0.997	189	87.6	338
	1.0	0.03	𝑦 = −4.655𝑥 + 6.308	0.996	38.7	82.3	−145
PEG-300	2.0	0.04	𝑦 = −5.385𝑥 + 8.930	0.999	44.8	81.8	−123
	3.0	0.05	𝑦 = −2.684𝑥 + 0.252	0.998	22.4	81.0	−195
	4.0	0.06	𝑦 = −8.743𝑥 + 20.63	0.999	72.7	80.5	−20.0
	5.0	0.08	𝑦 = −7.750𝑥 + 17.60	0.999	64.5	80.0	−51.3
	0.5	0.02	𝑦 = −6.979𝑥 + 13.65	0.999	58.0	83.3	−84.0
	1.0	0.03	𝑦 = −6.106𝑥 + 11.05	0.997	50.8	82.5	−105
PEG-400	2.0	0.04	𝑦 = −9.224𝑥 + 21.84	0.999	76.7	81.5	−16.0
	3.0	0.06	𝑦 = −8.718𝑥 + 20.54	0.999	72.5	38.0	−80.5
	4.0	0.07	𝑦 = −7.054𝑥 + 15.38	0.999	58.7	80.1	−69.7
	5.0	0.1	𝑦 = −7.687𝑥 + 17.63	0.999	64.0	79.3	−51.0
	0.5	0.02	𝑦 = −5.421𝑥 + 8.550	0.998	45.0	83.0	−126
	1.0	0.03	𝑦 = −4.644𝑥 + 6.274	0.999	38.6	82.2	−145
PEG-600	2.0	0.04	𝑦 = −3.131𝑥 + 1.542	0.999	26.0	81.4	−184
	3.0	0.05	𝑦 = −5.555𝑥 + 9.813	0.999	46.2	81.0	−115
	4.0	0.07	𝑦 = −3.622𝑥 + 3.753	0.998	30.1	80.0	−166
	5.0	0.1	𝑦 = −4.247𝑥 + 5.956	0.999	35.3	80.0	−148