In SEC (or GPC) the number- /weight- or z-average molar mass is calculated for the whole injected sample (whole distribution) or should it be calculated for each peak individually? Thank you!
Your question seems simple, but the answer is complicated because the analysis problem is actually sophisticated.
A sample containing polymeric materials can be a mixture of homologous series (homopolymer), or of materials with varying architecture (branching), or varying composition (copolymer composition or a simple mixture), or all of the above.
There are several questions which could be considered: Are the two peaks the same polymer with the same composition and architecture ?
If the answer is yes, then the overall moments of the entire envelope represent the sample and its properties best. If, on the other hand, the goal is to understand the composition or polymerization effects, then having the two separate moments of the distributions can be very informative.
If the answer is questionable, then analysis of the fractions needs to be done before an appropriate calculation can be made. The sample could be a mixture of different polymers, different branching, different colpolymer composition, or and combination of the above. Fractionation and analysis of the fractions (e.g. IR, UV, Viscometry, light scattering) will reveal the answer(s) to those questiions. This fractionation/analysis is sometimes done online multiple detection, or off line by separate analysis of fractions collected from the separation..Once the true nature of the sample is defined, then the appropriate calculations can be made.