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 5

Activation parameters of nitrocinnamic 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 = −12.00𝑥 + 29.73	0.999	100	85.0	50.0
	1.0	0.02	y = −10.87𝑥 + 26.63	0.999	90.3	83.1	24.0
PEG-200	2.0	0.04	𝑦 = −4.711𝑥 + 6.807	0.999	39.2	37.05	−141
	3.0	0.06	𝑦 = −5.506𝑥 + 9.842	0.999	46.0	38.04	−116
	4.0	0.07	𝑦 = −5.012𝑥 + 8.347	0.999	42.0	38.40	−128
	5.0	0.09	𝑦 = −3.923𝑥 + 4.963	0.998	33.0	38.99	−156
	0.5	0.01	𝑦 = −9.764𝑥 + 22.25	0.999	81.2	85.0	−13.0
	1.0	0.02	𝑦 = −7.861𝑥 + 16.58	0.999	65.4	83.3	−60.0
PEG-300	2.0	0.04	𝑦 = −4.270𝑥 + 5.297	0.999	35.5	37.0	−153
	3.0	0.05	𝑦 = −6.852𝑥 + 14.13	0.999	57.0	81.0	−80.0
	4.0	0.06	𝑦 = −6.545𝑥 + 13.3	0.998	54.4	81.2	−89.5
	5.0	0.08	𝑦 = −9.042𝑥 + 21.84	0.999	75.1	80.0	−16.0
	0.5	0.02	𝑦 = −7.717𝑥 + 16.10	0.977	64.1	83.2	−64.0
	1.0	0.03	𝑦 = −5.321𝑥 + 8.612	0.999	44.2	82.0	−126
PEG-400	2.0	0.04	𝑦 = −8.683𝑥 + 20.01	0.999	72.1	81.4	−31.2
	3.0	0.06	𝑦 = −8.718𝑥 + 20.54	0.999	72.4	80.4	−27.0
	4.0	0.07	𝑦 = −7.947𝑥 + 18.23	0.998	66.0	80.0	−46.0
	5.0	0.10	𝑦 = −7.687𝑥 + 17.63	0.999	64.0	79.3	−51.0
	0.5	0.01	𝑦 = −9.635𝑥 + 21.82	0.998	80.1	85.0	−16.2
	1.0	0.02	𝑦 = −8.534𝑥 + 18.80	0.997	71.0	83.4	−41.3
PEG-600	2.0	0.04	𝑦 = −4.071𝑥 + 4.648	0.999	34.0	82.0	−159
	3.0	0.06	𝑦 = −4.703𝑥 + 7.167	0.999	39.1	80.5	−138
	4.0	0.08	𝑦 = −3.635𝑥 + 3.891	0.999	30.2	80.0	−165
	5.0	0.10	𝑦 = −5.600𝑥 + 10.65	0.999	46.5	79.2	−109