Transformer steel (Fe-6 at. pct Si) was doped with varying amounts of phosphorus and given an embrittling step-cool heat treatment. Auger electron spectroscopy was used to determine that large increases in intergranular phosphorus concentration occurred in approximate proportion to the bulk phosphorus level through an equilibrium segregation mechanism. Bicrystals of this material were fractured at 300, 77 and 4.2 K. Grain boundary fracture energy, γgb was determined as a function of intergranular phosphorus concentration at 4.2 K. An analysis of γgband fracture mode, as a function of temperature, was used to evaluate the relative merits of intergranular fracture models based on reduced interatomic separation energy (Gibbs-Griffith model) and reduced interatomic cohesive strength (Seah model). It was found that the reduced interatomic separation energy model best fits the experimental findings.