Glass compositions xPbO : 20Na2O : (80-x)B2O3 (x = 5,10,15,20,25,30,35,40,45,50 and 55 %mol) have been prepared using melt-quenching method. The density and molar volume of these glass samples have been found to be compositional dependent. The results indicate that PbO acts on the glass structures were different between the range 0≤ x ≤ 20 %mol and beyond x = 20 %mol (with inflection at x = 20 %mol). These due to the PbO can enter the glass network both as a network modifier and also as a network former. This role depends on the type of bond between lead and oxide. These results are interpreted in term of IR analysis.