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By Carey F., Sundberg R.

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D ϩ 2F (add steps 1, 2, and 3). 2A ϩ C (1) unimolecular, (2) bimolecular, (3) bimolecular. Rate ϭ k[C][A], since A is needed to make the intermediate, B. See Fig. 6. 41 is 2E G. What is G? A side product. 43 The rate expression for the reaction (CH3)3C⎯Br ϩ CH3COOϪ ϩ Agϩ CH3COOC(CH3)3 ϩ AgBr is Rate ϭ k[(CH3)3C —Br][Agϩ] Suggest a plausible two-step mechanism showing the reacting electrophiles and nucleophiles. The rate-determining step involves only (CH3)3C⎯Br and Agϩ. The acetate ion CH3COOϪ must participate in an ensuing fast step.

The ions are solvated by more H2O molecules than is CH3COOH. When ions form molecules, many of these H2O molecules are set free and therefore have more randomness (SP > SR ). 11 Predict the most stable state of H2O (steam, liquid, or ice) in terms of (a) enthalpy, (b) entropy, and (c) free energy. Liquid Solid are exothermic processes and, therefore, ice has the least enthalpy. For this rea(a) Gas son, ice should be most stable. Liquid Gas shows increasing randomness and therefore increasing entropy.

H of a chemical reaction is the difference in the enthalpies of the products, Hp, and the reactants, HR : ΔH ϭ HP Ϫ HR If the bonds in the products are more stable than the bonds in the reactants, energy is released, and ΔH is negative. The reaction is exothermic. (3) ΔS is the change in entropy. Entropy is a measure of randomness. The more the randomness, the greater is S; the greater the order, the smaller is S. For a reaction: ΔS ϭ SP Ϫ SR (4) ΔG ϭ GP Ϫ GR is the change in free energy. At constant temperature: ΔG ϭ ΔH Ϫ TΔS (T ϭ Absolute temperature) For a reaction to be spontaneous, ΔG must be negative.

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