AbstractHeats of mixing of n‐pentane, n‐decane and n‐tridecane with benzene were experimentally determined at 25d̀C. Values of the parameters associated with the quasi‐lattice theory were evaluated using the experimental results together with the literature heats of mixing values for the systems benzene‐n‐hexane, benzene‐n‐heptane, benzene‐n‐octane, benzene‐n‐nonane and benzene‐n‐hexadecane. Using the literature model for benzene, the values of the parameters for the n‐alkanes that resulted in the “best fit” of the experimental data differ from those reported in the literature. A set of parameter values is reported which permits the evaluation of heats of mixing values for binary benzene‐n‐alkane systems within an average absolute deviation of 3.6%, with the except