LECTURE4AOSCCHEM637AtmosphericChemistryR.Dickerson.pptVIP

? R. R. Dickerson 2011 Lecture 4 Summary Changes in enthalpy and entropy, DH and DS, are nearly independent of temperature. Gibbs free energy provides the criterion of feasibility. The residence time (lifetime), t, is the inverse of the first order rate constant, k. If second or third order reactions can be approximated as first order then lifetimes can be estimated. For reversible reactions, kf/kr = Keq * * * * * * * * * * * 3. Third Order A + B + C ? PRODUCTS d[A]/dt = -k[A][B][C] Examples 2NO + O2 = 2NO2 O + O2 + M = O3 + M? M is any third body (usually N2) needed to dissipate excess energy. From the ideal gas law and Avgs number: Where Mo is the molecular number density at STP in molecules cm-3. Third order rate constants have units of conc-2 time-1. These are usually (cm-3)-2 s-1. kNO-O2 = 2.0 x 10-38 cm6 s-1 kO-O2 = 4.8 x 10-33 cm6 s-1 * Useful idea: For the following reversible reaction: A + B ? C + D d[C]/dt = kf [A][B] - kr [C][D] At steady state d[C]/dt = 0, by definition. Thus: * Half-life and Lifetime Definition: Half-life, t1/2, is the time t such that: [A]t / [A]0 = 1/2 Definition of e-folding lifetime or residence time, ? , comes from kinetics, where k is the first order rate constant with units of time-1. We know that: [A]t/[A]0 = exp(-kt) The lifetime, ?, is when t = 1/k so ? ? 1/k We can link half-life and lifetime: t1/2 = ln(2)/k ? 0.69/k For radon 222 (222Rn) the lifetime is 5.5 days, but the half-life is only 3.8 days. ? = (k[ā])-1 * For second and third order reactions we can sometime approximate first order conditions – or use pseudo first order kinetics. A + B → Prod. If [B] [A] Then k[B] is approximately constant. We call this pseudo first order rate constant k’. * For second and third order reactions we can sometime approximate first order conditions – or use pseudo first order kinetics. For example: NO + O3 ? NO2 + O2 k = 1.9 x 10-14 cm3 s-1 Assume: [O3] [NO] and d[O3]/dt ~ 0.