Silver nitrate chemical ionization for analysis of hydrocarbon polymers by laser desorption fourier transform mass spectrometry.

Addition of silver nitrate to nonpolar hydrocarbon polymer solutions prior to their analysis by laser desorption Fourier transform mass spectrometry is shown to allow efficient silver ion chemical ionization. High-quality mass spectra are thus obtained for polymers, such as polystyrene, polyisoprene, polybutadiene, and polyethylene, that previously failed to yield useful mass spectra using conventional laser desorption. Accurate mass measurement experiments and isotopic ratios verify that the spectra are those of silver-attached oligomer ion distributions. Mass measurement errors for complete oligomer distributions average between 3 and 12 ppm for oligomers with masses between 400 and 6000 D whereas unit mass resolution is maintained throughout the entire spectral range.