equation predicts that, in a nucleophilic displacement on benzyl chloride, the azide anion reacts 3000 times faster than water. Ritchie equation The Ritchie equation, derived in 1972, is another free-energy relationship: where N+ is the nucleophile dependent parameter and k0 the reaction rate constant for water. In this equation, a substrate-dependent parameter like s in the Swain–Scott equation is absent. The equation states that two nucleophiles react with the same relative reactivity regardless of the nature of the electrophile, which is in violation of the reactivity–selectivity principle. For this reason, this equation is also called the constant selectivity relationship. In the original publication the data were obtained by reactions of selected nucleophiles with selected electrophilic carbocations such as tropylium or diazonium cations: or (not displayed) ions based on malachite green. Many other reaction types have since been described. Typical Ritchie N+ values (in methanol) are: 0.5 for methanol, 5.9 for the cyanide anion, 7.5 for the methoxide anion, 8.5 for the azide anion, and 10.7 for the thiophenol anion. The values for the relative cation reactivities are −0.4 for the malachite green cation, +2.6 for the benzenediazonium cation, and +4.5 for the tropylium cation. Mayr–Patz equation In the Mayr–Patz equation (1994): The second order reaction rate constant k at 20 °C for a reaction is related to a nucleophilicity parameter N, an electrophilicity parameter E, and a nucleophile-dependent slope parameter s. The constant s is defined as 1 with 2-methyl-1-pentene as the nucleophile. Many of the constants have been derived from reaction of so-called benzhydrylium ions as the electrophiles: and a diverse collection of π-nucleophiles: . Typical E values are +6.2 for R = chlorine, +5.90 for R = hydrogen, 0 for R = methoxy and −7.02 for R = dimethylamine. Typical N values with s in parenthesis are −4.47 (1.32) for electrophilic aromatic substitution to toluene (1), −0.41 (1.12) for electrophilic addition to 1-phenyl-2-propene (2), and 0.96 (1) for addition to 2-methyl-1-pentene (3), −0.13 (1.21) for reaction with triphenylallylsilane (4), 3.61 (1.11) for reaction with 2-methylfuran (5), +7.48 (0.89) for reaction with isobutenyltributylstannane (6) and +13.36 (0.81) for reaction with the enamine 7. The range of organic reactions also include SN2 reactions: With E = −9.15 for the S-methyldibenzothiophenium ion, typical nucleophile values N (s) are 15.63 (0.64) for piperidine, 10.49 (0.68) for methoxide, and 5.20 (0.89) for water. In short, nucleophilicities towards sp2 or sp3 centers follow the