Despite the remarkable success of Carnot’s heat engine cycle in founding the discipline of thermodynamics two centuries ago, false viewpoints of his use of the caloric theory in the cycle still linger, limiting his legacy. An action revision of the Carnot cycle can correct this, showing that the heat flow powering external mechanical work is compensated internally with configurational changes in the thermodynamic or Gibbs potential of the working fluid, differing in each stage of the cycle quantified by Carnot as caloric. Action (@) is a property of state having the same physical dimensions as angular momentum (mrv=mr2ω). However, this property is scalar rather than vectorial, including a dimensionless phase angle (@=mr2ωδφ). We have recently confirmed with atmospheric gases that their entropy is a logarithmic function of the relative vibrational, rotational and translational action ratios with Planck’s quantum of action ħ. The Carnot principle shows that the maximum rate of work (puissance motrice) possible from the reversible cycle is controlled by the difference in temperature of the hot source and the cold sink, the colder the better. This temperature difference between the source and the sink also controls the isothermal variations of the Gibbs potential of the working fluid, that Carnot identified as reversible temperature-dependent but unequal exchanges in caloric. Importantly, the engine’s inertia ensures that heat from work performed adiabatically in the expansion phase is all restored to the working fluid during the adiabatic recompression, less the net work performed. This allows both the energy and the thermodynamic potential to return to the same values at the beginning of each cycle, a point strongly emphasized by Carnot. Our action revision equates Carnot’s calorique, or the non-sensible heat later described by Clausius as ‘work-heat’ exclusively to negative Gibbs energy (-G) or quantum field energy. This action field complements the sensible energy or vis-viva heat as molecular kinetic motion and its recognition should have significance for designing more efficient heat engines or better understanding of the heat engine powering the Earth’s climates.

A testable hypothesis with quantitative predictions is put forward, proposing that strong acids produced on land are a major cause of increasing atmospheric pCO2. Our modelling analysis of reactions by dissolved inorganic carbon shows that increasing atmospheric CO2 could be caused thermodynamically by falling land surface pH values. This hypothesis challenges the imbalance assumed between the global uptake of CO2 by photosynthesis and emissions of CO2 from all sources, including the combustion of fossil fuels. Strong acids generated by oxygen from reduced nitrogen and sulphur emits CO2 almost stoichiometrically from dissolved bicarbonate in the pH range of most global soils from pH 6.5 to above 8. Each general decrease of aqueous pH value of 0.01 units from acidification of surface water potentially increases the pCO2 in the atmosphere by about 7 ppmv. Contrary to prevailing assumptions that CO2 emissions from combusting fossil fuels can remain in the atmosphere for more than a millennium, such emissions may be partly nullified by global greening from enhanced rates of photosynthesis as well as oceanic absorption. The surface pH value of the ocean has been shown to decrease as atmospheric pCO2 rises. Therefore, our qualitative estimates of increasing atmospheric CO2 driven by irreversible acidification on land are critical and need broad scale validation. To the extent that significant acidification of the land is occurring, through export of alkaline produce, the use of artificial nitrogen fertilisation and possible other causes, the prevailing methods of reducing CO2 emissions will fail. However, these acidifying processes on land have not been considered by previous biogeochemical reviews. Despite counter measures, including carbon capture and geological storage, the increasing Keeling curve for pCO2 may continue to rise because zero carbon policies do not address such a major cause. This hypothesis can be tested by in situ experiments in neutral soils and water, designed to compare CO2 emissions under the acidifying conditions described in this article with those when corrective counter measures are applied.