This report details our assessment of the chemistry of the planned Hanford Waste Vitrification Plant (HWVP) off-gas system and its impact on the applicability of known iodine removal and control methods. To predict the gaseous species in the off-gas system, we completed thermodynamic calculations to determine theoretical equilibrium concentrations of the various potential chemical species. In addition, we found that HWVP pilot-plant experiments were generally consistent with the known chemistry of the individual elements present in the off gas. Of the known trapping techniques for radioiodine, caustic scrubbing and silver-containing sorbents are, in our opinion, the most attractive methods to reduce the iodine concentration in the HWVP melter off gas (MOG) after it has passed through the high-efficiency particulate air (HEPA) filter. These two methods were selected because they (1) have demonstrated retention factors (RFs), ratio of amount in and amount out, of 10 to 1000, which would be sufficient to reduce the iodine concentration in the MOG to below regulatory limits; (2) are simple to apply; (3) are resistant to oxidizing gases such as NOx; (4) do not employ highly hazardous or highly corrosive agents; (5) require containment vessels constructed or common materials; (6) have received extensive laboratory development; (7) and the radioactive wastes produced should be easy to handle.