A particle entering a scattering and absorbing medium executes a random walk through a sequence of scattering events. The particle ultimately either achieves first-passage, leaving the medium, or it is absorbed. The Kubelka–Munk model describes a flux of such particles moving perpendicular to the surface of a plane-parallel medium with a scattering rate and an absorption rate. The particle path alternates between the positive direction into the medium and the negative direction back towards the surface. Backscattering events from the positive to the negative direction occur at local maxima or peaks, while backscattering from the negative to the positive direction occur at local minima or valleys. The probability of a particle avoiding absorption as it follows its path decreases exponentially with the path-length λ. The reflectance of a semi-infinite slab is therefore the Laplace transform of the distribution of path-length that ends with a first-passage out of the medium. In the case of a constant scattering rate the random walk is a Poisson process. We verify our results with two iterative calculations, one using the properties of iterated convolution with a symmetric kernel and the other via direct calculation with an exponential step-length distribution. We present a novel demonstration, based on fluctuation theory of sums of random variables, that the first-passage probability as a function of the number of peaks n in the alternating path is a step-length distribution-free combinatoric expression involving Catalan numbers. Counting paths with backscattering on the real half-line results in the same Catalan number coefficients as Dyck paths on the whole numbers. Including a separate forward-scattering Poisson process results in a combinatoric expression related to counting Motzkin paths. We therefore connect walks on the real line to discrete path combinatorics.