AbstractThe consecutive reactions of (CH3)2Si(OC2H5)2and CH3Si(OC2H5)3with methoxide ions were investigated in methanol solutions. The reverse transesterification reactions with ethoxide ions could be neglected in both cases since the concentration of ethoxide in methanol solution was assumed to be low due to the fast equilibrium reaction C2H5O−+ CH3OH ⇌ C2H5OH + CH3O−. The progress of the reactions was followed by monitoring the formation of ethanol with a Fourier‐transform infrared spectrometer. All rate constants were determined at 295 K. The reactions between the dialkoxydimethylsilanes and methoxide ions were assumed to consist of two consecutive steps that can be represented by the net reaction; (CH3)2Si(OC2H5)2+ 2CH3O−→ (CH3)2Si(OCH3)2+ 2C2H5O−. The two consecutive rate constants were established as 1.93 ± 0.12M−1s−1and 1.00 ± 0.12M−1s−1, respectively. The consecutive rate constants for the reactions between the trialkoxymethylsilanes and methoxide ions can be written according to the total reaction; CH3Si(OC2H5)3+ 3CH3O−→ CH3Si(OCH3)3+ 3C2H5O−. The three rate constants corresponding to each consecutive step were established as 1.12 ± 0.09 M−1s−1, 0.82 ± 0.10 M−1s−1, and 0.51 ± 0.06 M−1s−