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The applicability of diffusion theory for the determination of tissue optical properties from steady-state diffuse reflectance is investigated. Analytical expressions from diffusion theory using the two most commonly assumed boundary conditions at the air-tissue interface and the two definitions of the diffusion coefficient are compared with Monte Carlo simulations. The effects of the choice of the boundary conditions and diffusion coefficients on the accuracy of the findings for the optical parameters are quantified, and criteria for accurate curve-fitting algorithms are developed. It is shown that the error in deriving the optical coefficients is considerably smaller for the solution which uses the extrapolated boundary condition and the diffusion coefficient independence of absorption coefficient, compared to the other three solutions.