An on-board catalytic monitoring system uses an intrusive technique to cause the vehicle's engine to cycle between first and second operating conditions. The first and second operating conditions are chosen such that different concentrations of emissions with different chemistries are present at the first and second operating conditions. A calorimetric sensor with a selective catalyst senses exothermic oxidation reactions produced by the emissions in the exhaust gas passing over the sensor. By matching the catalyst activity with the emission concentrations occurring at the operating conditions, the difference between the heat release sensor signals detected between the first and second operating conditions is indicative of the actual concentration of specific emissions in the exhaust gas stream. The difference or delta signal, obtained without reference to a zero point, provides an excellent correlation to the efficiency of the vehicle's catalytic converter for converting the sensed emission, i.e., hydrocarbons.