Thermodynamics of irreversible processes is applied to study the interaction of matter and radiation field in nonlocal thermodynamic equilibrium. The rate of entropy production of matter and radiation field, in contact with a free electron reservoir in local thermodynamic equilibrium, is obtained using the conjugate variables of the state variables. When approximating the electronic configuration populations by an effective Boltzmann law, the corresponding effective temperature is determined by minimizing the rate of entropy production at fixed electronic density, electronic temperature, and radiation field. Numerical results and comparisons with recent experiment for photoionized iron plasma are presented and discussed.