Global Warming by Geothermal Heat from Fracking: Energy Industry's Enthalpy Footprints.

Hypothetical dry adiabatic lapse rate (DALR) air expansion processes in atmosphere climate models that predict global warming cannot be the causal explanation of the experimentally observed mean lapse rate (approx.−6.5 K/km) in the troposphere. The DALR hypothesis violates the 2nd law of thermodynamics. A corollary of the heat balance revision of climate model predictions is that increasing the atmospheric concentration of a weak molecular transducer, CO2, could only have a net cooling effect, if any, on the biosphere interface temperatures between the lithosphere and atmosphere. The greenhouse-gas hypothesis, moreover, does not withstand scientific scrutiny against the experimental data. The global map of temperature difference contours is heterogeneous with various hotspots localized within specific land areas. There are regional patches of significant increases in time-average temperature differences, (∆) = 3 K+, in a ring around the arctic circle, with similar hotspots in Brazil, South Africa and Madagascar, a 2−3 K band across central Australia, SE Europe centred in Poland, southern China and the Philippines. These global-warming map hotspots coincide with the locations of the most intensive fracking operational regions of the shale gas industry. Regional global warming is caused by an increase in geothermal conductivity following hydraulic fracture operations. The mean lapse rate (d/dz)z at the surface of the lithosphere will decrease slightly in the regions where these operations have enhanced heat transfer. Geothermal heat from induced seismic activity has caused an irreversible increase in enthalpy (H) input into the overall energy balance at these locations. Investigating global warming further, we report the energy industry's enthalpy outputs from the heat generated by all fuel consumption. We also calculate a global electricity usage enthalpy output. The global warming index, <∆T-biosphere> since 1950, presently +0.875 K, first became non-zero in the early 1970's around the same time as natural gas usage began and has increased linearly by 0.0175 K/year ever since. Le Chatelier's principle, applied to the dissipation processes of the biosphere's ΔH-contours and [CO2] concentrations, helps to explain the global warming statistics.

Disquisitions Relating to Principles of Thermodynamic Equilibrium in Climate Modelling.

We revisit the fundamental principles of thermodynamic equilibrium in relation to heat transfer processes within the Earth's atmosphere. A knowledge of equilibrium states at ambient temperatures (T) and pressures (p) and deviations for these p-T states due to various transport 'forces' and flux events give rise to gradients (dT/dz) and (dp/dz) of height z throughout the atmosphere. Fluctuations about these troposphere averages determine weather and climates. Concentric and time-span average values (z, Δt)) and its gradients known as the lapse rate = d < T(z) >/dz have hitherto been assumed in climate models to be determined by a closed, reversible, and adiabatic expansion process against the constant gravitational force of acceleration (g). Thermodynamics tells us nothing about the process mechanisms, but adiabatic-expansion hypothesis is deemed in climate computer models to be convection rather than conduction or radiation. This prevailing climate modelling hypothesis violates the 2nd law of thermodynamics. This idealized hypothetical process cannot be the causal explanation of the experimentally observed mean lapse rate (approx.−6.5 K/km) in the troposphere. Rather, the troposphere lapse rate is primarily determined by the radiation heat-transfer processes between black-body or IR emissivity and IR and sunlight absorption. When the effect of transducer gases (H2O and CO2) is added to the Earth's emission radiation balance in a 1D-2level primitive model, a linear lapse rate is obtained. This rigorous result for a perturbing cooling effect of transducer ('greenhouse') gases on an otherwise sunlight-transducer gas-free troposphere has profound implications. One corollary is the conclusion that increasing the concentration of an existing weak transducer, i.e., CO2, could only have a net cooling effect, if any, on the concentric average (z = 0) at sea level and lower troposphere (z < 1 km). A more plausible explanation of global warming is the enthalpy emission 'footprint' of all fuels, including nuclear.

Supercritical Fluid Gaseous and Liquid States: A Review of Experimental Results.

We review the experimental evidence, from both historic and modern literature of thermodynamic properties, for the non-existence of a critical-point singularity on Gibbs density surface, for the existence of a critical density hiatus line between 2-phase coexistence, for a supercritical mesophase with the colloidal characteristics of a one-component 2-state phase, and for the percolation loci that bound the existence of gaseous and liquid states. An absence of any critical-point singularity is supported by an overwhelming body of experimental evidence dating back to the original pressure-volume-temperature (p-V-T) equation-of-state measurements of CO2 by Andrews in 1863, and extending to the present NIST-2019 Thermo-physical Properties data bank of more than 200 fluids. Historic heat capacity measurements in the 1960s that gave rise to the concept of "universality" are revisited. The only experimental evidence cited by the original protagonists of the van der Waals hypothesis, and universality theorists, is a misinterpretation of the isochoric heat capacity Cv. We conclude that the body of extensive scientific experimental evidence has never supported the Andrews-van der Waals theory of continuity of liquid and gas, or the existence of a singular critical point with universal scaling properties. All available thermodynamic experimental data, including modern computer experiments, are compatible with a critical divide at Tc, defined by the intersection of two percolation loci at gaseous and liquid phase bounds, and the existence of a colloid-like supercritical mesophase comprising both gaseous and liquid states.

Thermodynamics of Tower-Block Infernos: Effects of Water on Aluminum Fires.

We review the thermodynamics of combustion reactions involved in aluminum fires in the light of the spate of recent high-profile tower-block disasters, such as the Grenfell fire in London 2017, the Dubai fires between 2010 and 2016, and the fires and explosions that resulted in the 9/11 collapse of the World Trade Center twin towers in New York. These fires are class B, i.e., burning metallic materials, yet water was applied in all cases as an extinguisher. Here, we highlight the scientific thermochemical reasons why water should never be used on aluminum fires, not least because a mixture of aluminum and water is a highly exothermic fuel. When the plastic materials initially catch fire and burn with limited oxygen (O2 in air) to carbon (C), which is seen as an aerosol (black smoke) and black residue, the heat of the reaction melts the aluminum (Al) and increases its fluidity and volatility. Hence, this process also increases its reactivity, whence it rapidly reacts with the carbon product of polymer combustion to form aluminum carbide (Al4C3). The heat of formation of Al4Cl3 is so great that it becomes white-hot sparks that are similar to fireworks. At very high temperatures, both molten Al and Al4C3 aerosol react violently with water to give alumina fine dust aerosol (Al2O3) + hydrogen (H2) gas and methane (CH4) gas, respectively, with white smoke and residues. These highly inflammable gases, with low spontaneous combustion temperatures, instantaneously react with the oxygen in the air, accelerating the fire out of control. Adding water to an aluminum fire is similar to adding "rocket fuel" to the existing flames. A CO2-foam/powder extinguisher, as deployed in the aircraft industry against aluminum and plastic fires by smothering, is required to contain aluminum fires at an early stage. Automatic sprinkler extinguisher systems should not be installed in tower blocks that are at risk of aluminum fires.

Thermodynamic Fluid Equations-of-State.

As experimental measurements of thermodynamic properties have improved in accuracy, to five or six figures, over the decades, cubic equations that are widely used for modern thermodynamic fluid property data banks require ever-increasing numbers of terms with more fitted parameters. Functional forms with continuity for Gibbs density surface ρ(p,T) which accommodate a critical-point singularity are fundamentally inappropriate in the vicinity of the critical temperature (Tc) and pressure (pc) and in the supercritical density mid-range between gas- and liquid-like states. A mesophase, confined within percolation transition loci that bound the gas- and liquid-state by third-order discontinuities in derivatives of the Gibbs energy, has been identified. There is no critical-point singularity at Tc on Gibbs density surface and no continuity of gas and liquid. When appropriate functional forms are used for each state separately, we find that the mesophase pressure functions are linear. The negative and positive deviations, for both gas and liquid states, on either side of the mesophase, are accurately represented by three or four-term virial expansions. All gaseous states require only known virial coefficients, and physical constants belonging to the fluid, i.e., Boyle temperature (TB), critical temperature (Tc), critical pressure (pc) and coexisting densities of gas (ρcG) and liquid (ρcL) along the critical isotherm. A notable finding for simple fluids is that for all gaseous states below TB, the contribution of the fourth virial term is negligible within experimental uncertainty. Use may be made of a symmetry between gas and liquid states in the state function rigidity (dp/dρ)T to specify lower-order liquid-state coefficients. Preliminary results for selected isotherms and isochores are presented for the exemplary fluids, CO2, argon, water and SF6, with focus on the supercritical mesophase and critical region.

Renaissance of Bernal's random close packing and hypercritical line in the theory of liquids.

We review the scientific history of random close packing (RCP) of equal spheres, advocated by J D Bernal as a more plausible alternative to the non-ideal gas or imperfect crystal as a structural model of simple liquids. After decades of neglect, computer experiments are revealing a central role for RCP in the theory of liquids. These demonstrate that the RCP amorphous state of hard spheres can be well defined, is reproducible, and has the thermodynamic status of a metastable ground state. Further evidence from simulations of square-well model liquids indicates an extended role of RCP as an amorphous ground state that terminates a supercooled liquid coexistence line, suggesting likewise for real liquids. A phase diagram involving percolation boundaries has been proposed in which there is no merging of liquid and gas phases, and no critical singularity as assumed by van der Waals. Rather, the liquid phase continuously spans all temperatures, but above a critical dividing line on the Gibbs density surface, it is bounded by a percolation transition and separated from the gas phase by a colloidal supercritical mesophase. The colloidal-like inversion in the mesophase as it changes from gas-in-liquid to liquid-in-gas can be identified with the hypercritical line of Bernal. We therefore argue that the statistical theory of simple liquids should start from the RCP reference state rather than the ideal gas. Future experimental priorities are to (i) find evidence for an amorphous ground state in real supercooled liquids, (ii) explore the microscopic structures of the supercritical mesophase, and (iii) determine how these change from gas to liquid, especially across Bernal's hypercritical line. The theoretical priority is a statistical geometrical theory of RCP. Only then might we explain the coincident values of the RCP packing fraction with Buffon's constant, and the RCP residual entropy with Boltzmann's ideal gas constant.

Thermodynamic description of liquid-state limits.

A state of random close packing (RCP) of spheres is found to have a thermodynamic status and a fundamental role in the description of liquid-state equilibria. The RCP limiting amorphous ground state, with reproducible density and well-characterized structure, is obtained by well-defined irreversible and reversible processes. The limiting packing fraction y(RCP) = 0.6366 ± 0.0005 (Buffon's constant within the uncertainty), and a residual entropy per sphere ΔS((RCP-FCC)) is approximately equal to k(B) (Boltzmann's constant). Since the Mayer virial expansion does not represent dense fluid equations-of-state for densities exceeding the available-volume percolation transition (ρ(pa)), we infer that a RCP state belongs to the same thermodynamic phase as prepercolation equilibrium dense hard-sphere fluid and likewise for hard-core fluids with attractive forces. Monte Carlo (MC) calculation of the liquid-state coexistence properties of square-well (SW) attractive spheres, together with existing MC results for liquid-vapor coexistence in the SW fluid, support this conclusion. Further findings for liquid-vapor coexistence limits are reported. The extremely weak second-order available-volume percolation transition of the hard-sphere fluid is strengthened by square-well perturbation as temperature is reduced. At the critical temperature, this transition becomes first order, whereupon a liquid at the percolation density coexists in thermodynamic equilibrium with its vapor at a lower density. The critical coexisting vapor density relates to the extended-volume bonded cluster percolation transition ρ(pe)(λ) defined for given well width (λ). Taking experimental liquid argon data as an example, it can be seen that the thermodynamic description of the coexistence limits, found here for square-well fluids, applies to real liquids.

Thermodynamic pressures for hard spheres and closed-virial equation-of-state.

Hard-sphere molecular dynamics (MD) simulation results, with six-figure accuracy in the thermodynamic equilibrium pressure, are reported and used to test a closed-virial equation-of-state. This latest equation, with no adjustable parameters except known virial coefficients, is comparable in accuracy both to Padé approximants, and to numerical parameterizations of MD data. There is no evidence of nonconvergence at stable fluid densities. The virial pressure begins to deviate significantly from the thermodynamic fluid pressure at or near the freezing density, suggesting that the passage from stable fluid to metastable fluid is associated with a higher-order phase transition; an observation consistent with some previous experimental results. Revised parameters for the crystal equation-of-state [R. J. Speedy, J. Phys.: Condens. Matter 10, 4387 (1998)] are also reported.

Density functional approach to thermodynamics of self-assembly.

A local density functional approximation for predicting the surface crystallization of a thermodynamically small system under gravity is described and tested. Using the model of the classical soft-sphere fluid, the state parameters for such systems are identified. A generalized phase diagram based upon the scaling variables is obtained; systems with the same reduced-state parameters exhibit identical profiles of thermodynamic properties such as density, pressure, and intrinsic chemical potential, measured in the direction of the applied field. The point-thermodynamic approximation of Rowlinson and the local density approximation of the density functional formalism are found to be remarkably accurate. A configurational temperature is defined and shown to agree with the corresponding kinetic temperature for inhomogeneous systems at equilibrium. The structural profiles at the crystal-fluid interface are indicative of a mesolayer of lower density crystal, not seen in the field-free isobaric crystal-liquid interface.