When adding a fourth substance to a system of three at thermal equilibrium, the temperature of thermal equilibrium can be determined using energy conservation principles. If the fourth substance is at the same temperature as the others, the system remains in thermal equilibrium. To find the final equilibrium temperature, one must consider the specific heat capacities and initial temperatures of the existing substances. The total energy before and after the addition must remain equal for accurate calculations. Thus, knowing the temperature of thermal equilibrium is essential for solving the problem correctly.