The effect of the chemical composition of titanium enamels on the type of phosphate groupings formed and the whiteness of enamel coatings is examined. It established that in glasses with an elevated mass content of glass-forming cations, specifically, about 60% SiO2, the phosphorus-containing grouping formed binds up to two alkali cations, and for 50% SiO2 phosphate groupings with one alkali cation are predominately formed.