This Thesis covers work conducted to understand the mechanisms underpinning the operation of the electrothermal-chemical gun. The initial formation of plasma from electrically exploding wires, through to the development of plasma venting from the capillary and interacting with a densely packed energetic propellant bed is included. The prime purpose of the work has been the development and validation of computer codes designed for the predictive modelling of the elect rothe rmal-ch em ical (ETC) gun. Two main discussions in this Thesis are: a proposed electrically insulating vapour barrier located around condensed exploding conductors and the deposition of metallic vapour resulting in a high energy flux to the surface of propellant, leading to propellant ignition. The vapour barrier hypothesis is important in a number of fields where the passage of current through condensed material or through plasma is significant. The importance may arise from the need to disrupt the fragments by applying strong magnetic fields (as in the disruption of metallic shaped charge jets); in the requirement to generate a metallic vapour efficiently from electrically exploding wires (as per ETC ignition systems); or in the necessity to re-use the condensed material after a discharge (as with lightning divertor strips). The ignition by metallic vapour deposition hypothesis relies on the transfer of latent heat during condensation. It is important for the efficient transfer of energy from an exploded wire (or other such metallic vapour generating device) to the surface of energetic material. This flux is obtained far more efficiently through condensation than from radiative energy transfer, because the energy required to evaporate copper is far less than that required to heat it to temperatures at which significant radiative flux would be emitted