Initial rates. A new plot

Excellent estimations of initial rates can be obtained from plots of delta P/t versus product formed (where P is the instantaneous concentration of the product). delta P/t is the chord from P0,t0 to P,t on an ordinary P-versus-t plot. When the chord is plotted as a function of product, the intercept at P0 of the resulting curve is necessarily dP/dt0. This curve approximates to a straight line extremely closely in all cases tested thus far. If delta P/t versus product is calculated from the integrated rate equation for a first-order reaction, and if a straight line is fitted through points representing the first 50% of the reaction, the discrepancy between the true initial rate and dP/dt0 estimated from the plot is 0.68%. For the most common form of the integrated rate equation for catalysed reactions the discrepancy varies between 0 and 0.90%. Because of the complexities of the integrated rate equations, catalysed second-order reactions have not been evaluated directly; uncatalysed reactions have been done instead. For a reaction with one reactant and two products, the discrepancy varies from 0.68 to 2.02%. For two reactants and one product, it varies from 0 to 0.68%; for two and two, 0 to 2.02%. The larger discrepancies occur only when unfavourable equilibrium constants are being overcome by the initial conditions.