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 4

Activation parameters of methoxy cinnamic acid in different PEG media. Units of 𝑘^′′ = dm³mol⁻¹min⁻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 = −12.85𝑥 + 32.55	0.996	107	85.0	73.0
	1.0	0.02	𝑦 = −13.90𝑥 + 36.01	0.998	115	84.4	102
PEG-200	2.0	0.04	𝑦 = −6.038𝑥 + 11.21	0.999	50.2	81.50	−104
	3.0	0.06	𝑦 = −5.027𝑥 + 8.448	0.999	42.0	80.2	−127
	4.0	0.08	𝑦 = −3.844𝑥 + 4.748	0.999	32.0	80.0	−158
	5.0	0.12	𝑦 = −4.403𝑥 + 6.945	0.999	37.0	79.0	−140
	0.5	0.01	𝑦 = −10.36𝑥 + 14.11	0.997	86.0	35.3	110
	1.0	0.03	𝑦 = −3.532𝑥 + 2.653	0.999	46.0	98.5	−175
PEG-300	2.0	0.04	𝑦 = −5.385𝑥 + 8.930	0.959	45.0	82.0	−123
	3.0	0.05	𝑦 = −2.423𝑥  − 0.582	0.999	20.2	78.0	−192
	4.0	0.06	𝑦 = −8.743𝑥 + 20.63	0.999	73.0	81.0	−26.0
	5.0	0.08	𝑦 = −7.965𝑥 + 18.28	0.999	66.2	80.0	−46.0
	0.5	0.02	𝑦 = −7.638𝑥 + 15.83	0.999	63.5	83.3	−66.0
	1.0	0.03	𝑦 = −10.01𝑥 + 24.07	0.999	83.2	77.0	21.3
PEG-400	2.0	0.04	𝑦 = −9.756𝑥 + 23.58	0.999	81.0	81.4	−2.0
	3.0	0.06	𝑦 = −8.022𝑥 + 18.16	0.999	67.0	80.0	−41.0
	4.0	0.08	𝑦 = −6.000𝑥 + 11.86	0.999	50.0	80.0	−99.0
	5.0	0.10	𝑦 = −9.302𝑥 + 22.89	0.999	77.3	79.5	−7.3
	0.5	0.02	𝑦 = −7.936𝑥 + 16.83	0.999	66.0	83.3	−58.0
	1.0	0.03	𝑦 = −5.955𝑥 + 10.61	0.998	49.5	82.3	−110
PEG-600	2.0	0.05	𝑦 = −4.894𝑥 + 7.616	0.999	41.0	81.3	−134
	3.0	0.06	𝑦 = −6.259𝑥 + 12.33	0.999	52.0	80.5	−95.0
	4.0	0.08	𝑦 = −5.659𝑥 + 10.63	0.999	47.0	38.72	−110
	5.0	0.1	𝑦 = −6.719𝑥 + 14.05	0.998	56.0	80.3	−81.0