In this paper, we attempt to understand the physico-chemical changes that occur in devices during device "burn-in". We discuss the use of low frequency dielectric spectroscopy to detect, characterize and monitor changes in electrical defects present in the dielectrics of through silicon vias (TSV) for three dimensional (3D) interconnected integrated circuit devices, as the devices are subjected to fluctuating thermal loads. The observed changes in the electrical characteristics of the interconnects were traceable to changes in the chemistry of the isolation dielectric used in the TSV construction. The observed changes provide phenomenological insights into the practice of burn-in. The data also suggest that these "chemical defects" inherent in the 'as-manufactured' products may be responsible for some of the unexplained early reliability failures observed in TSV enabled 3D devices.