Using low energy electron microscopy, we have investigated the (2×1)-(1×1) phase transition occurring above 925 K on Ge(001). Dimer breakup has been identified as the physical origin of this transition. A quantitative description of the dimer concentration during the transition involves configuration entropy of random monomers within the dimer matrix. The dimer formation energy amounts to 1.2±0.3 eV. Dimer breakup promotes reversible surface disorder by step proliferation and irreversible surface roughening above 1130 K.