Heat defect (calorimetry) 2026-11-05
The heat defect in water calorimetry measures the fraction of absorbed energy that does not appear as heat because of radiation-induced chemical changes. Writing absorbed energy as and the energy appearing as heat as , the convention used by Norman V. Klassen and Carl K. Ross isA positive value means less heat than the absorbed-energy equivalent; a negative value means the chemical response adds heat.[ref]
Water Calorimetry: The Heat Defect by Norman V. Klassen and Carl K. Ross. Printed p.63, Eqs1–2 and accompanying definition.
If other thermal corrections are treated separately, the absorbed dose isAn illustrative means that represents 98% of the dose, so the chemical correction multiplies that thermal estimate by . The example fixes a sign convention; it is not a measured universal value for water.
The motivating evidence included variations with dissolved gases and comparison of radiolysis calculations with chemical measurements of hydrogen peroxide. Those tests address chemical energy accounting. An external heat leak or a drifting thermometer can also alter a temperature reading, but belongs to a different correction mechanism.[ref]
Water Calorimetry: The Heat Defect by Norman V. Klassen and Carl K. Ross. Abstract and Introduction: radiolysis model and independently measured chemical product.
Norman V. Klassen 2026-11-05
Norman V. Klassen is a physicist whose work with Carl K. Ross connects water calorimetry, radiolysis and absorbed dose measurement. Their 1997 study compared calculated heat defects with experimental observations, including independently measured chemical products. This comparison tests the physical model through more than its agreement with a single temperature rise.[ref]
Water Calorimetry: The Heat Defect by Norman V. Klassen and Carl K. Ross. Printed p.63, byline, Abstract and Introduction
The issue is that a water calorimeter measures a thermal response to ionizing radiation, whereas absorbed dose concerns deposited energy per unit mass. If is the thermal energy per unit mass, the heat defect relates them byA useful sensitivity calculation follows directly. Holding fixed and differentiating with respect to givesFor an illustrative , an absolute change changes the inferred absorbed dose by approximately , or . Thus improving thermometer precision alone cannot remove the contribution of an uncertain heat defect to measurement uncertainty. The example is a local sensitivity estimate, rather than an uncertainty budget for their apparatus.[ref]
Water Calorimetry: The Heat Defect by Norman V. Klassen and Carl K. Ross. Printed p.63, Eq1, from which the sensitivity calculation follows
In 2002, Klassen and Carl K. Ross reported that a literature reaction rate constant used in their earlier model was incorrect and supplied a revised model. Their correction also compared model predictions with calorimetric and chemical-product measurements. It illustrates why the inputs to a computer simulation are part of the scientific claim: agreement must be reassessed when those inputs are corrected.[ref]
Water Calorimetry: A Correction to the Heat Defect Calculations by Norman V. Klassen and Carl K. Ross. Printed p.171, Abstract and Introduction