Table 4.

Calculated ΔG^≠ (kcal mol⁻¹), tunnelling corrections (κ), the nuclear reorganization energy (λ, kcal mol⁻¹) rate constants (k_app, k_f, and k_overall M⁻¹ s⁻¹), molar fractions (f) and branching ratios (Γ, %) at 298.15 K, in the SFR + HOO^• reaction in pentyl ethanoate and water solvents.

mechanism		pentyl ethanoate				water
		ΔG≠	κ	kapp	Γ	ΔG≠	κ	kapp	f	kf**	Γ
SET						6.6	15.6*	8.90 × 107	0.460	4.09 × 107	86.2
HAT	O3′−H	15.0	106.9	6.90 × 103	38.5	16.0	744.5	9.20 × 103	0.540	4.97 × 103	0.0
	O4′−H	14.9	163.1	1.10 × 104	61.5	15.5	202.8	5.30 × 103	0.540	2.86 × 103	0.0
	O3′−H (anion)					7.8	1.2	1.42 × 107	0.460	6.53 × 106	13.7
koverall				1.79 × 104						4.75 × 107

*λ; **k_f = f.k_app; Γ = k.100/k_overall.