A chemical multiplication reaction is a reaction sequence in which a species is converted through a cycle into more of that same species before measurement. Unlike a one-time conversion to a different reporter, the multiplied species can enter another cycle. IUPAC calls the case involving the species being determined a direct multiplication reaction.[ref]
Let be the amount of the multiplied species after cycle . If every cycle has the same net multiplier , then
For an original ideal example, and four cycles convert into . The gain is 81, not 12: repeating a threefold increase compounds it. The stoichiometry concerns a sequence supplied with reagents, rather than multiplication of isolated molecules without additional matter.
A multiplication-cycle yield changes the net multiplier. Suppose a fraction of the entering species completes a route producing three output molecules, while the remaining fraction survives unchanged. Then
For stipulated , four cycles give gain , substantially below 81. If failed molecules are instead destroyed, the model would give : specifying the fate of failures is essential. For cycle-dependent multipliers, the gain is , not a fixed power by assumption.
The same compounding can affect an initial chemical amplification blank. Tenfold less contaminant at the start need not stay negligible after many cycles, and contamination introduced late experiences fewer cycles. Reagent depletion, side reactions and changing yield limit the range over which a constant-gain measurement calibration is credible. Cycle number and blank history belong in the experimental record.
A multiplication-cycle yield specifies how successfully a cycle of a chemical multiplication reaction converts entering material into the intended output. It must state what happens to material that fails to complete the route. A stoichiometric multiplier alone is insufficient to determine the achieved gain.
Suppose successful processing produces copies of the measured species per entering copy, the success fraction is , and a fraction of unsuccessful material survives unchanged. The net cycle multiplier is
Here represents survival of all failures and destruction of all failures. In an original example, and give when failures survive, but when they are lost. After five cycles the gains are approximately 118.8 and 79.6. The chemistry's failure pathway materially affects the answer.
For different cycle yields, total gain is . IUPAC's ideal direct-multiplication description gives for repeated identical cycles; the variable-yield expression follows by applying each cycle in sequence.[ref]
Cycle-gain uncertainty depends strongly on whether cycle errors are shared. Taking small perturbations,
For independent multipliers with the same relative standard uncertainty , the relative uncertainty of is approximately . If one uncertain multiplier applies identically to every cycle, it is approximately . With and , these models give 3% and 9%, respectively. Repeating a shared error is different from averaging independent errors.[ref]
Measure standards over the intended cycle range, with matched chemical amplification blanks. Reagent depletion, side reactions or inhibition can make the actual multiplication-cycle yield change with time or amount. A nominal gain calculated from ideal stoichiometry does not replace that experimental test.