Linear step-growth molecule count ($N=N_0-J$)

Use an ideal feed in which every starting molecule has exactly two suitable functional groups: either one $A$ and one $B$, or two $A$ groups mixed with two $B$ groups. Only an $A$–$B$ pairing can form a joining chemical bond. Assume no loss of feed-derived material, no splitting of chains, no competing consumption of the counted functional groups, no branching, and no cyclization in step-growth polymerization. Linear here describes connectivity; a chain can bend in space. Small byproducts of polycondensation do not enter the chain-bearing molecule count.

Let $N_0$ count all initial feed molecules, $J$ the number of intermolecular joins, and $N$ all remaining chain-bearing molecules, including unreacted monomers. Each join turns two molecules into one, so $N=N_0-J$ exactly. If chain $i$ contains $j_i$ feed-derived monomeric units, conservation gives ${\sum }_{i=1}^N{j}_i=N_0$. Consequently the number-average degree of polymerization isThis is a count of both feed species' monomeric units, rather than a count of interior constitutional repeating units. For $AA+BB$ chemistry an interior repeat often contains two feed-derived units, as explained in monomer. Equal functional group reactivities are not needed for this bookkeeping at a specified $J$; predicting a time course or a chain-length probability distribution requires additional assumptions.

For the figure's eight $AB$ feed molecules, three joins can give lengths $(2,3,1,1,1)$, so $N=5$ and $X_n=8/5$. Joining the first two chains gives $(5,1,1,1)$: the incorporated total stays eight, $N$ becomes four, and $X_n=2$. A graph makes the bookkeeping visible: each starting monomer molecule is a vertex of a graph, and each intermolecular joining chemical bond connects two previously distinct connected components of a graph. The connected pieces are the counted molecules.

In a balanced bifunctional feed there are initially $N_0$ $A$ groups and $N_0$ $B$ groups. Define the functional-group conversion in step growth by $p=J/N_0$: the reacted fraction of either group type. Each join consumes one of each. Therefore $N=N_0(1-p)$. In the eight-$AB$ example, three joins give $p=3/8$ and four give $p=1/2$. In the latter state only three of eight starting monomer molecules remain isolated: their disappearance fraction is $5/8$, different from $p=1/2$. Neither this group-based $p$ nor disappearance of isolated monomers is the incorporated-feed fraction in the ideal living polymerization count.

With unequal initial counts $A_0\le B_0$, this article always uses $p=J/A_0$, the conversion of the limiting $A$ groups. The reacted fraction of $B$ groups is $J/B_0=rp$, where $r=A_0/B_0$. The fraction of all initial functional groups consumed is $2J/(A_0+B_0)=2rp/(1+r)$. At nonzero conversion these three fractions coincide only at $r=1$. Naming the measured group type prevents an apparently correct equation from using the wrong conversion.