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 3

Activation parameters of crotonic 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 = −9.907𝑥 + 22.7	0.999	82.4	85.1	−9.0
	1.0	0.02	𝑦 = −6.742𝑥 + 12.86	0.999	56.0	83.3	−91.0
PEG-200	2.0	0.03	𝑦 = −5.069𝑥 + 7.688	0.999	42.1	82.3	−134
	3.0	0.04	𝑦 = −6.020𝑥 + 11.13	0.999	50.0	81.5	105
	4.0	0.05	𝑦 = −7.664𝑥 + 16.87	0.999	64.0	81.2	−57.3
	5.0	0.06	𝑦 = −7.062𝑥 + 14.92	0.999	59.0	81.0	−73.5
	0.5	0.01	𝑦 = −9.797𝑥 + 22.35	0.999	81.4	85.0	−12.0
	1.0	0.02	𝑦 = −8.070𝑥 + 17.25	0.999	67.0	83.2	−54.2
PEG-300	2.0	0.04	𝑦 = −4.233𝑥 + 5.180	0.998	35.2	81.5	−154
	3.0	0.05	𝑦 = −6.852𝑥 + 14.13	0.999	54.6	79.0	−80.0
	4.0	0.06	𝑦 = −6.564𝑥 + 13.36	0.999	54.5	80.4	−86.5
	5.0	0.08	𝑦 = −9.440𝑥 + 23.13	0.999	78.5	80.0	−5.3
	0.5	0.01	𝑦 = −9.759𝑥 + 22.23	0.999	81.2	85.0	−13.0
	1.0	0.02	𝑦 = −7.864𝑥 + 16.59	0.999	65.4	83.3	−57.0
PEG-400	2.0	0.04	𝑦 = −4.189𝑥 + 5.034	0.999	35.0	82.0	−155
	3.0	0.05	𝑦 = −8.018𝑥 + 17.93	0.999	67.0	81.5	−48.5
	4.0	0.06	𝑦 = −5.394𝑥 + 9.454	0.999	45.0	80.7	−119
	5.0	0.08	𝑦 = −8.250𝑥 + 19.25	0.998	68.6	80.0	−37.5
	0.5	0.01	𝑦 = −9.630𝑥 + 21.81	0.998	80.0	85.0	−16.3
	1.0	0.02	𝑦 = −5.541𝑥 + 8.852	0.998	46.0	83.2	−123
PEG-600	2.0	0.03	𝑦 = −5.256𝑥 + 8.404	0.999	44.0	82.3	−128
	3.0	0.04	𝑦 = −5.421𝑥 + 9.243	0.998	45.0	81.2	−120
	4.0	0.06	𝑦 = −4.492𝑥 + 6.466	0.997	37.4	80.5	−144
	5.0	0.09	𝑦 = −6.254𝑥 + 12.73	0.999	52.0	80.0	−91.8