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Equations for heat and mass transfer in membrane distillation (MD) have been developed and tested experimentally. The concept of temperature polarisation is introduced and shown to be important in the interpretation of experimental results. Vapour transport through the membranes tested is reasonably described by combined Knudsen and molecular diffusion. The significance of temperature polarisation in the design and operation of large-scale MD modules is discussed, and hollow fibre and tubular systems shown to be potentially the most effective.