The physical and mechanical properties of rocks can be reduced significantly by an acidic environment, resulting in engineering weaknesses, such as building foundation instability, landslides, etc. In order to investigate the mechanical properties of rocks after hydrochemical erosion, a chemical damage constitutive model was established and used to analyze chemical damage variables and energy transformation. It is assumed that the strength of the rock elements obeyed Weibull distribution, considering the nonuniformity of rock. The chemical damage variable was proposed according to the load-bearing volume changes in the rock under water–rock chemical interactions. The chemical damage constitutive model was derived from coupling the mechanical damage under the external load and the chemical damage under hydrochemical erosion. In order to verify the accuracy of the model, semi-immersion experiments and uniaxial compression experiments of black sandy dolomite were carried out with different iron ion concentrations. Compared with the experimental data, the chemical damage constitutive model proposed could predict the stress–strain relationship reasonably well after water–rock interaction. The effects of water–rock interaction on the rock were a decrease in peak stress and an increase in peak strain. The peak strain increased by 4.96–29.58%, and the deterioration rate of peak strength was 0.19–4.18%. The energy transformation of the deterioration process was analyzed, and the results showed that the decrease in releasable elastic energy, Ue, is converted into dissipated energy, Ud, after hydrochemical erosion.
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