Microscopic thermodynamic studies can elucidate specific molecular interactions. In this work, we report the microscopic thermodynamics in binary liquid mixtures, which elucidate the role of molecular structure in nonlinear solvent response using femtosecond optical tweezers (FOT). We obtain the excess thermodynamics property of mixing in various Newtonian liquid mixtures by analyzing Microrheology data from FOT. Using our noninvasive 780 nm pulse laser we have trapped micron-sized particles to show how excess viscosity and residual Gibbs free energy change due to mixing. Furthermore, we establish from this study that hydrocarbon chain length and branching can modulate microscopic thermodynamics through intermolecular interaction. This work sheds light on the relationship between thermodynamic properties and viscosity, which is of immense importance for predicting transport properties, mixing, and chemical reactions.

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