BrightSpec: FT-MRR Instruments for Trace VOC Analysis (Fourier Transform - Molecular Rotational Resonance) Brooks H. Pate, CTO and Bob Lloyd, CEO © 2014 BrightSpec, Inc. 770 Harris St. Suite 104B, Charlo=esville, VA 22903 BrightSpec Instruments Direct Analysis of Gas Mixtures Multispecies Trace Detection Analysis of Gas Sample Impurities BrightSpec instruments measure the molecular rotaIonal spectrum of molecules in a low pressure gas. The spectrum is directly related to the three dimensional structure through the moments-‐of-‐inerIa. The rotaIonal spectrum provides the most selecIve chemical signature in molecular spectroscopy. The combinaIon of high measurement sensiIvity and high spectral resoluIon enables the direct quanItaIve analysis of gas mixtures without the need for chemical separaIon (Gas Chromatography). User programmable measurement protocols can be used to perform mulIspecies trace detecIon for a set of target compounds. The broadband detecIon capabiliIes of FT-‐MRR spectroscopy can be used to analyze gas sample purity. Quantitative Multispecies Analysis 2 I = MR High Sensitivity with Broad Molecule Coverage For direct analysis of gases, FT-MRR spectroscopy offers the sensitivity of dedicated spectroscopy sensors like cavity ring down spectroscopy (CRDS). Different mass distributions have different signatures making it easy to distinguish isomers and isotopologues. Detection of Trace Concentrations and Trace Amounts The rotational spectrum of gases at room-temperature falls in the mmwave/THz frequency range making it possible to use solid-state electronics as light sources. Expanded scale view of spectrum (full range 260 -290 GHz) and the instrument panel for mixture analysis in the Edgar control software. Molecule Measured Concentra4on Actual Concentra4on Ethylene Oxide 42.3% 41.8% + 1.2% Propyne 19.2% 18.7% + 1.2% VOLATILE Carbonyl Sulﬁde 18.7% 18.7% + 1.2% Triﬂuoroiodomethane 10.7% 11.7% + 1.2% High resoluIon MRR spectroscopy requires freely rotaIng molecules at reduced pressure (10-‐4 atm). Only 1mL of STP gas is required. Chloroethane 8.2% 7.0% + 1.2% 1-‐Butyne 1.34% 2.3% + 1.2% Molecular Properties for FT-MRR Spectroscopy POLAR LOW MASS Stronger coupling between the electric ﬁeld of the excitaIon light and the oscillaIng dipole means stronger signals. DetecIon sensiIvity is opImal for rigid molecules with mass up to 150 amu. Gases Cylinder purity Process control Environmental Monitoring Analysis of a commercial sample of CF3I shows a 1% impurity from CF3H. The black spectrum trace is the commercial sample. The blue (CF3I) and green (CF3H) spectra are the BrightSpec FTMRR library spectra used to analyze the sample. Solids Liquids Headspace Analysis Residual Solvent IdenIﬁcaIon TGA Detection Limits for Molecules in the BrightSpec FT-MRR Spectral Library EsImated SensiIvity Limits: BrightSpec Library Chemical Hydrogen Cyanide Acetonitrile Carbonyl Sulﬁde Ethylene Oxide Acrylonitrile Phosphine Triﬂuoromethane Propionitrile Acetaldehyde Vinyl Chloride Propyne Methyl Isocyanate Propionacetaldehyde Dichloromethane LDL (pmol in 40s) 0.027 0.04 0.13 0.19 0.26 0.27 0.27 0.4 0.54 1.1 1.1 1.1 1.1 1.3 LDL (pbb in 40s) 10 15 50 70 100 100 100 150 200 400 400 400 400 500 Chemical Chloroethane g-‐Butyrolactone Methanesufonyl chloride Methanol Acetone Chloroacetonitrile Ethanol Formaldehyde (in water) 2-‐propanol Iodotriﬂuoromethane 1-‐Butyne 1-‐propanol Propylene Chloroform LDL (pmol in 40s) LDL (pbb in 40s) 1.3 500 2.3 850 2.4 900 2.7 1000 4.1 1500 4.7 1800 6.8 2500 9.4 3500 11 4000 13 5000 20 7500 41 15000 54 20000 67 25000 Site-Specific Isotope Analysis The combination of sensitivity and spectral resolution make it possible to analyze the stable isotopes of molecules. Each isotopologue has a characteristic spectrum. FT-MRR spectroscopy analyzes low pressure gases (10-100 mTorr) and has detection limits of 1 pmol or lower for many chemical species. Analysis of Isotopes in Natural Abundance The spectral signatures from isotopologues are easily resolved with FT-MRR spectroscopy because each site uniquely changes the mass distribution. Factor of 1000 Sensitivity Enhancement with Preconcentration Using established preconcentration methods a detection limit of 100 ppt is achieved for phosphine (PH3). All in One Instrument Site-specific isotope analysis is possible for larger molecules even where there are only subtle differences in the molecular structure that distinguishes the atomic sites. Example Capabilities N2O: OCS: 14N14N16O, 15N14N16O, 14N15N16O, 14N14N17O, 14N14N18O 16O12C32S, 17O12C32S, 18O12C32S, 16O13C32S, 16O12C33S, 16O12C34S NH3: 14NH 3, 15NH 3, 14NH 2D SO2: 16O32S16O, 17O32S16O, 18O32S16O, 16O33S16O, 16O34S16O All in One Instrument