Materials with an intensity dependent index of refraction and absorption coefficient—third-order optical non-linear (ONL) effects—offer the possibility of all-optical signal processing. Prism coupling is a well-known tool to investigate the intensity dependent refractive index, however, such experiments are often obscured by thermal effects. To avoid these we have studied the influence of the ONL effects on the shape of 70 ps pulses in non-linear prism coupling. The full width at half maximum (FWHM) of the in and out coupled pulses is compared simultaneously with the FWHM of the pulses of a reference beam. By measuring at various angles of incidence around that for optimal coupling it is possible to measure the sign and value of the change in both the refractive index and absorption coefficient. As a function of the coupling angle, the first leads to an asymmetric line shape for the ratio of the two FWHMs mentioned above, whereas the second leads to a symmetric one. From a comparison of simulations with experimental data, the values of the non-linear constants can be derived.