Quantitative absorption spectroscopy of residual water vapor in high-purity gases: pressure broadening of the 1.39253-microm H2O transition by N2, HCl, HBr, Cl2, and O2.
We determined the respective pressure-broadening coefficients of HCl, HBr, Cl2, and O2 (expressed relative to that of the reference gas N2) for the (v1,v2,v3)J(Ka,Kc) = (0,0,0)3(0,3) --> (1,0,1)2(0,2) rovibrational transition of H2 16O that occurs at 1.39253 microm. The experiment used a continuous-wave cavity ring-down spectroscopy analyzer to measure the peak absorption losses as a function of added moisture concentration. The measured pressure-broadening coefficients for HCl, HBr, Cl2, and O2 are, respectively, 2.76, 2.48, 1.39, and 0.49 times that of the N2 pressure-broadening coefficient, and detection limits for water vapor range from 0.22 nmol mol(-1) for O2 matrix gas to 2.3 nmol mol(-1) for HBr matrix gas. The degradation of the detection limit (relative to the N2 matrix gas) is ascribed to a pressure-broadening-induced reduction in peak absorption cross section and to elevated background loss from the matrix gas.