Table 1.

Rates and thermodynamics of NP and DNP hydrolysis in water, acetone, and cyclohexane

		Observed rate constantsd				Catalysis by desolvatione				Transfer of substratef				Phase transfer rateg
		ΔG‡	ΔH‡	TΔS‡	k25/s−1	ΔG‡	ΔH‡	TΔS‡	k25/s−1 M−1	ΔG	ΔH	TΔS	Keq	ΔG‡	ΔH‡	TΔS‡	kpt/s−1
DNP−	H2Oa	38.1	29.5	−8.6	7.0 × 10−16	40.5	29.5	−11.0	1.3 × 10−17	0	0	0	1	38.1	29.5	−8.6	7.0 × 10−16
	Acetone	32.9	22.6	−10.3	3.9 × 10−12	32.6	22.6	−10.0	7.0 × 10−12	—	—	—	—	—	—	—	—
	CHX	31.0	19.6	−11.4	1.0 × 10−10	27.8	19.6	−8.2	2.4 × 10−8	6.0	32.4	26.4	3.9 × 10−5	37.4	52	14.6	3.9 × 10−15
NP2−	H2Ob	44.3	47.0	2.7	2.0 × 10−20	47.7	47.0	−0.7	3.6 × 10−22	0	0	0	1	44.3	47.0	2.7	2.0 × 10−20
	CHXc	32.9	47.6	14.7	3.8 × 10−12	29.7	47.6	17.9	9.0 × 10−10	7.1	11.3	4.2	7.0 × 10−6	40.0	59.2	19.3	2.4 × 10−17

^aFrom ref. 1.

^bFrom ref. 14.

^cFrom ref. 4.

^dObtained from Arrhenius plots constructed with experimentally measured rates.

^eObtained from Arrhenius plots constructed with second order rate constants obtained by dividing experimentally measured rate constants by the concentration of water present in the reaction medium (Fig. 1).

^fTransfer coefficients measured for the extraction of the substrate from water to cyclohexane. Values obtained from van’t Hoff plots constructed with experimentally measured transfer coefficients (ESI^†).

^gObtained as described in ref. 4. This value represents the combination of substrate extraction from water (“transfer of substrate” column) and phosphate ester hydrolysis (“observed rate constants” column).