Is There the Fourth Law of the Thermodynamics?

Abstract

The Gibbs energy change ∆ G in half-reactions Me →Me n+ + ne and halogens 1/2Hal2 + e → Hal- were analyzed using cycles∆ G Me = ∆ G subl. + ∑ I - ∆ G hydr. - W e (1)∆ G Hal = ∆G dissoc. - E affinity - ∆ G hydr. + W e (2)including energies of metal sublimation +∆G subl. , ionization of metal vapor +∑I , chemical hydration of Me n+ ions -∆G hydr. , condensation of free electrons from vacuum onto electrode - W e ; dissociation of halogen molecules + ∆G dissoc. , acceptance of electrons from vacuum by halogens - E affinity, chemical hydration of Hal- anions -∆G hydr. , abstraction of electrons from electrode into vacuum + W e. [1,2].The Gibbs energy ∆G* Me and ∆G* Hal were calculated using known constants Eqns. (3, 4) [1]∆ G* Me = ∆ G subl. + ∑ I - ∆ G hydr. (3)∆ G* Hal = 1/2 ∆ G dissoc. - E affinity - ∆ G hydr. (4)The relations between ∆G*/ n by Eqns. (3), (4), n - number of electrons, for metals and halogens (electron bonds decrease in them) and corresponding standard potentials Eo are linear and extrapolated to Eo = - 4.72 V SHE at ∆G*/ n = 0 (Fig.1;lines 1, 2).Calculated ∆G*/ n = 4.95 eV (Cu)and ∆G* = -5.27 eV (I2 ) are close in value (Fig.1). According to Eqns. (1, 2), ∆G/ n in half-reactions of weak reductant Cu and oxidant I 2 should tend to zero (metals - non-metals transition).For this, calculated ∆G* = 4.95 eV (Cu)and ∆G* = -5.27 eV (I2 ) should be decreased and increased on W e ~ 5.1 - 5.2 eV respectively [1,2].The intermediate W e,interm. = 5.19 eV is determined to some substance (metals - non-metals transition) which electrons should be bound by non-specific (non-chemical) definite Coulomb bond [2, 3].The linear relations for metals (line 1) and halogen (line 2) are displaced in the parallel direction by -5.19 and 5.19 eV respectively (Fig.1) when account is taken W e,interm. = 5.19 eV, i.e., we obtained linear relations 1’ and 2’ between ∆G/ n of chemical half-reactions by Eqns. (1, 2) and their Eo . Relations 1’ and 2’ intersect with E o – axis at ∆G/ n = 0 at potential Eo = ~ + 0.47 V SHE close to Billiter potential + 0.475 V SHE corresponded by [1-3] to hypothetical electrode between metals and non-metals without own chemical activity or to chemical equilibrium half-reactions.According to Eqns. (3, 4), limiting separated electrons (vacuum) and ions without any bonding are formed from metals, non-metals with spending decreased ∆G*/ n (lines 1, 2, Fig.1). When ∆G*/ n = 0 ( Eo = - 4.72 V SHE), all components of Eqns. (3) and (4) are degenerated. For such a system ∆G* = - A max = 0, the entropy change is equal ∆ S = 0. Hence, the entropy S tends to constant and infinity S max → ∞.The Gibbs energy ∆G*/ n = 5.19 eV (Fig.1)of limiting separation of definite Coulomb bound electrons – ions (transfer + 0.475 V SHE → - 4.72 V SHE) per electron5.19 eV x 1.6021 x 10-19 J/eV = 8.314899 x 10-19 J (5)and the gas constant R = 8.31441 J/mol.K have equal bases.Then, R = 8.3144 J/mol. K is sufficient for limiting separation per 1 K of 1019 such non-chemically bound electrons - ions ( W e,interm. = 5.19 eV; Eo = + 0.475 V SHE, Fig.1). These electrons - ions should be analogous to non - chemically interacting particles of ideal gas at STP conditions.The energy R Δ T is equal to the energy 5.19 eV = 500703.548 J/mol of limiting separation of definite Coulomb bound electrons – ions at the change of temperature Δ T Δ T = 5.19 eV / 8.3144 J/mol K = 500703.548 J/mol / 8.3144 J/mol K = = 60221.25 K (6)which the base corresponds to Avogadro number and mole of limiting separated electrons – ions is equal to6.022 . 104 K x 1019 mol-1 K-1 = 6.022.1023 mol-1 (7)Hence, the origin of Avogadro number is number of electrons - ions condensing from limiting separated state (without bonding) to their state with non-chemical definite Coulomb bonds (analogous ideal gas).The 4th thermodynamics law: limiting separated state of electrons - ions with entropy S max →∞ occurs with increasing temperature on Δ T = 6.022 . 104 K from STP, at 6.022. 104 oC. The released heat leads only to increase in kinetic energy and temperature of limiting separated electrons - ions.Reference1.A.I.Chernomorskii, Zh. Fiz. Khim., 52, 757 (1978).2.A.I.Chernomorkii, The Intermediate Electron Bond and Half-reactions (Scientific Resources, New Yopk, NY) (1999).3.A.I.Chernomorkii, Journal of The Electrochemical Society, 2021,168, 116514. Figure 1