Differential absorption radiometry (DAR), using uncooled detectors, is a simple, low-cost method for passive remote sensing of hazardous chemicals for domestic security applications. However, radiometric temperature differences (ΔTeffective) between a target gas species and its background affect detection sensitivity. Two DARs with sensitivities to methanol, diisopropyl methylphosphonate (DIMP), and dimethyl methylphosphonate (DMMP), all spectral or physical simulants of hazardous chemicals, were developed and used to experimentally determine the effect of |ΔTeffective| on detection sensitivity. An analytical model was also developed and compared with the experimental results. With a signal-to-noise ratio (SNR)<5, a |ΔTeffective|≥2 K is sufficient for rapid (≤1 s) detection of methanol at <0.03 atm cm and DMMP and DIMP at <0.001 atm cm. These measured sensitivities suggest that rapid detection of hazardous chemical vapor clouds below lethal dose concentrations can be achieved using room-temperature pyroelectric detectors. Measurements were within 3% of the analytical predictions.