Smog chamber/Fourier transform infrared (FTIR) and laser-induced fluorescence (LIF) spectroscopic techniques were used to study the atmospheric degradation of CH3CHF2. The kinetics and products of the Cl(P-2(3/2)) (denoted Cl) atom- and the CH radical-initiated oxidation of CH3CHF2 in 700 Torr of air or N-2; diluents at 295 +/- 2 K were studied using smog chamber/FTIR techniques. Relative rate methods were used to measure k(Cl + CH3CHF2) = (2.37 +/- 0.31) x 10(-13) and k(OH + CH3CHF2) = (3.08 +/- 0.62) x 10(-14) cm(3) molecule(-1) s(-1). Reaction with Cl atoms gives CH3CF2 radicals in a yield of 99.2 +/- 0.1% and CH2CHF2 radicals in a yield of 0.8 +/- 0.1%. Reaction with OH radicals gives CH3CF2 radicals in a yield > 75% and CH2CHF2 radicals in a yield < 25%. Absolute rate data for the Cl reaction were measured using quantum-state selective LIF detection of Cl(P-2(j)) atoms under pseudo-first-order conditions. The rate constant k(Cl + CH3CHF2) was determined to be (2.54 +/- 0.25) x 10(-13) cm(3) molecule(-1) s(-1) by the LIF technique, in good agreement with the relative rate results. The removal rate of spin-orbit excited-state Cl*(P-2(1/2)) (denoted Cl*) in collisions with CH3CHF2 was determined to be k(Cl* + CH3CHF2) = (2.21 +/- 0.22) x 10(-10) cm(3) molecule(-1) s(-1). The atmospheric photooxidation products were examined in the presence and absence of NOx. In the absence of NOx, the Cl atom-initiated oxidation of CH3CHF2 in air leads to formation of COF2 in a molar yield of 97 +/- 5%. In the presence of NOx, the observed oxidation products include COF2 and CH3COF. As [NO] increases, the yield of COF2 decreases while the yield of CH3COF increases, reflecting a competition for CH3CF2O radicals. The simplest explanation for the observed dependence of the CH3COF yield on [NOx] is that the atmospheric degradation of CH3CF2H proceeds via OH radical attack to give CH3CF2 radicals which add O-2 to give CF3CF2O2 radicals. Reaction of CH3CF2O2 radicals with NO gives a substantial fraction of chemically activated alkoxy radicals, [CH3CF2O]*. In 1 atm of air, approximately 30% of the alkoxy radicals produced in the CH3CF2O2 + NO reaction possess sufficient internal excitation to undergo "prompt" (rate > 10(10) s(-1)) decomposition to give CH3 radicals and COF2. The remaining approximately 70% become thermalized, CH3CF2O, and undergo decomposition more slowly at a rate of approximately 2 x 10(3) s(-1). At high concentrations (> 50 mTorr), NO., is an efficient scavenger for CH3CF2O radicals leading to the formation of CH3COF and FNO.