We have studied the thermal interactions of acetone and acetaldehyde on Si(100), both sputtered and annealed, using high resolution electron energy loss spectroscopy, (HREELS), x-ray photoelectron spectroscopy (XPS), and temperature programmed desorption (TPD). There is no carbonyl stretch in HREELS and the C and O(1s) XPS peaks reflect two different carbonyl processes, one involving bond cleavage, the other a reduction of the C-O bond order. Hydrogen TPD gives a peak at 840-850 K which is as much as threefold more intense than from H-saturated Si(100). SiO desorbs near 1050 K and XPS shows total loss of oxygen and retention of carbon. Approximately 34% of the acetaldehyde monolayer and 62% of the acetone monolayer decomposes on annealed Si(100)to produce silicon carbide. In contrast, after sputtering with 500 eV Ar ions, these percentages are reduced to 14% and 25%, respectively. We conclude that Si dimers play an important role in the chemistry of carbonyl groups.