Final answer:
The main purpose of adding NaHCO₃(aq) to glassware contaminated with TMSCl is neutralizing acidity.
Step-by-step explanation:
The main purpose of adding NaHCO₃(aq) to glassware contaminated with TMSCl is neutralizing acidity. TMSCl is a strong acid and can be corrosive to glassware. NaHCO₃, also known as baking soda, is a basic compound. When it reacts with the acidic TMSCl, it neutralizes the acidity and helps to remove the contaminants from the glassware.