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 6

Activation parameters of acrylic 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 = −11.85𝑥 + 29.21	0.999	98.5	85.0	45.3
	1.0	0.02	𝑦 = −8.384𝑥 + 18.31	0.998	70.0	84.0	−45.3
PEG-200	2.0	0.03	𝑦 = −7.860𝑥 + 16.98	0.998	65.3	82.2	−57.0
	3.0	0.04	𝑦 = −8.164𝑥 + 18.27	0.997	68.0	82.0	−47.0
	4.0	0.06	𝑦 = −6.581𝑥 + 13.42	0.999	55.0	81.0	−86.0
	5.0	0.08	𝑦 = −6.061𝑥 + 11.96	0.998	51.0	80.5	−98.2
	0.5	0.01	𝑦 = −11.85𝑥 + 29.21	0.999	98.5	85.0	46.0
	1.0	0.02	𝑦 = −11.43𝑥 + 28.49	0.998	95.0	83.2	39.3
PEG-300	2.0	0.03	𝑦 = −10.67𝑥 + 26.25	0.997	89.0	83.0	21.0
	3.0	0.04	𝑦 = −9.163𝑥 + 21.61	0.999	76.2	82.0	−18.0
	4.0	0.05	𝑦 = −6.125𝑥 + 11.72	0.999	51.0	81.0	−100
	5.0	0.07	𝑦 = −5.443𝑥 + 9.792	0.998	45.3	80.2	−116
	0.5	0.02	𝑦 = −8.314𝑥 + 18.07	0.997	69.2	83.4	−47.4
	1.0	0.03	𝑦 = −9.364𝑥 + 21.98	0.998	78.0	82.5	−15.0
PEG-400	2.0	0.04	𝑦 = −9.756𝑥 + 23.58	0.999	81.2	82.0	−1.6
	3.0	0.06	𝑦 = −7.889𝑥 + 17.76	0.997	66.0	81.0	−50.0
	4.0	0.08	𝑦 = −6.573𝑥 + 13.69	0.998	55.0	80.2	−84.0
	5.0	0.10	𝑦 = −8.507𝑥 + 20.35	0.999	71.0	80.0	−28.4
	0.5	0.01	𝑦 = −9.947𝑥 + 22.82	0.998	83.0	85.4	−8.0
	1.0	0.02	𝑦 = −6.653𝑥 + 12.57	0.997	55.4	83.3	−93.0
PEG-600	2.0	0.03	𝑦 = −6.334𝑥 + 11.88	0.997	53.0	83.0	−99.0
	3.0	0.05	𝑦 = −2.362𝑥  − 0.780	0.998	20.0	77.4	−191
	4.0	0.07	𝑦 = −3.078𝑥 + 1.893	0.998	26.0	80.5	−182
	5.0	0.09	𝑦 = −4.666𝑥 + 7.455	0.998	39.0	80.0	−135