This work investigates the volatilities of amine solvents used in post-combustion CO₂ capture from coal-fired power plants. Amine volatility is one of the key criteria used in screening an amine solvent for CO₂ capture: (1) amine losses up the stack can react in the atmosphere to form ozone and other toxic compounds; (2) volatility losses can result in greater solvent make-up costs; (3) high losses will require the use of bigger water wash units, and more water, to capture fugitive amines prior to venting - these translate to higher capital and operating costs; (4) volatilities need to be measured and modeled in order to develop more accurate and robust thermodynamic models. In this work, volatility is measured using a hot gas FTIR which can determine amine, water, and CO₂ in the vapor headspace above a solution. The liquid solution is speciated by NMR (Nuclear Magnetic Resonance). There are two key contributions made by this research work: (1) it serves as one of the largest sources of experimental data available for amine-water volatility; (2) it provides amine volatility for loaded systems (where CO₂ is present) which is a unique measurement not previously reported in the literature. This work studied the volatility of 20 alkanolamines in water at 0.5 - 1.1 molal (m) in water (< 1.5 mol% amine) at zero loading (no CO₂) from 40 ° - 70 °C. An empirical group contribution model was developed to correlate H[subscript 'amine'] to molecular structures of both alkylamines and alkanolamines. The model incorporated additional functional groups to account for cyclic structures and to distinguish between different types of alkyl groups based on the attached neighboring groups. This model represented the experimental H[subscript 'amine'], which spanned five orders in magnitude, to well within an order of magnitude of the measured values. The second component of this research involves upgrading the AspenPlus® v.7.3 model of MDEA-PZ-CO₂-H₂O system primarily by improving MDEA thermodynamics for MDEA-H₂O, MDEA-CO₂-H₂O, and MDEA-PZ-CO₂-H₂O. A key modification was made to include the carbonate (CO₃²⁻) species into the model chemistry set which greatly improved the fit of CO₂ solubility for MDEA-CO₂-H₂O at ultra lean loading ([alpha]) for 0.001 < [alpha] < 0.01. With MDEA-PZ-H₂O, no MDEA-PZ cross interaction parameters were needed to match the blend volatility. Ultimately, both the blend volatility, at unloaded and loaded conditions, along with speciation were adequately represented by the upgraded model. The final component of this research involves screening the volatilities of novel amines at unloaded and nominal lean loading condition from 40 ° - 70 °C (absorber operating conditions). The volatility of tertiary and hindered amines, such as MDEA and AMP, respectively, is not a strong function of loading because these amines are unable to form stable carbamates. Conversely, the volatility of mono-amines and of diamines decreases by ~3 and 5-20 times, respectively, due to a much greater extent of carbamate-forming speciation. PZ or a blend having a diamine promoted by PZ would be favorable for CO₂ capture due to the low volatility of the diamines in loaded solution. . Finally, in order of increasing degree of salting out as reflected by the increasing magnitude of the system asymmetric amine activity coefficient, 7 m MDEA < 4.8 m AMP ~ 7 m MDEA/2 m PZ < 8 m PZ < 7 m MEA. / text