Ash agglomeration issues that arise due to the sticking of slag-wetted, colliding particles have been creating operational difficulties and monetary losses for the fluidized bed combustion (FBC) industry. Difficulties have been experienced in the detection of slag-liquid at the low operating temperatures in fluidized bed combustors (FBCs) and predicting the agglomeration behavior of fuel. This study aims to study the effect of heterogeneity in ash composition on the detection of slag-liquid in FBCs. It quantifies the slag-liquid amounts at the particle-level, under oxidizing environments, by dividing the bulk fuel into density classes. FactSage™ thermodynamic simulations of each of the particle classes, along with experimental validation of the trends with thermo-mechanical analysis (TMA) and high temperature X-ray diffraction (HT-XRD) were performed. The results obtained can be used to estimate the stickiness of particles in the development of ash agglomeration models based on particle collisions. The study of these particle classes shows that particle classes with specific minerals can form low temperature eutectics and lead to onset of slag-liquid formation at temperatures below those predicted by bulk analysis alone. Comparison of the differences in slag-liquid formation tendencies under reducing and oxidizing environments is also presented.