Influence of Magnetic Field on Chemical Reaction Kinetics

1. The influence of the magnetic field on the kinetic of the chemical reaction October 9th-12th, 2014 Pamporovo, BULGARIA Antonella De Ninno ENEA – Italian National Agency for New Technologies, Energy and Sustainable Economic Development

2. October 9th -12th, 2014 Pamporovo, BULGARIA Summary • The supra-molecular structure of liquid water • Non-isolated systems out of equilibrium • The effect of weak magnetic field on hydration of molecules • Low Energy/matter exchanges in aqueous systems

3. Röngten:floating low density clusters in high density matrix Bernal and Fowler : the revenge of the thermodynamics Linus Pauling: the idea of hydrogen bond Stanley and Teixeira the concept of infinite connected network or gel In the last decades a great number of Molecular Dynamics (MD) simulations have been carried on these bases. Robinson: domains of different density. The mixture model provides for the specific volume the simple expression: Philippa Wiggins and Martin Chaplin extended this two phase liquid concept to room temperature water in terms of: Low Density Water LDW is the hydrating water around cell membranes and DNA double helix and High Density Water HDW is the “bulk” water. Models of liquid water

4. Electrodynamic coherence Later on, the existence of water in two different populations made up by molecules having different degree of mutual correlation has been demonstrated according to first principles: it can be proved that when • the temperature T is lower than a critical Tcrit and the density N is higher than a critical Ncrit an ensemble of particles is subjected to a collective coherent oscillation between a couple of internal levels of its components, thus generating a • collective behaviour. These collective behaviour is responsible for the long-range forces which account for the actual existence of the condensed state.

5. Water represents a remarkable example of such a general principle: at room temperature a dynamical superposition of two populations, Fc , Fnc of coherent and non-coherent molecules is thereby established, depending on temperature. According to this view, each atom or molecule belongs to one of the two fractions in a dynamical sense, i.e. it fluctuates between a coherent and a non-coherent state with a characteristic time life ~ 5·10-15 sec. The coherent fraction represents the lowest energy, ordered state while the non coherent fraction is populated by monomers and dimers such as the gas phase. The vibrational spectra of liquid water can be easily interpreted in agreement with this theory . Very recent time-resolved optical Kerr effect investigation (pub, on Nature Comm.) have shown the evidence of the coexistence of two local configuration, interpreted as high density and low density water form from ambient to supercooled conditions

6. Non-isolated systems out of equilibrium • Nanoaggregates – Alexander Konovalov • EZ water – Jerry Pollack • Aquaphotomics – Roumiana Tsenkova • Stable aggregates of water at room temperature – Vittorio Elia • …

8. Actually, we know that the Temperature is not the only parameter influencing the fraction of coherent population: • Temperature (“ab initio” calculations) • Contact with surfaces (Pollack, Konovalov, Tsenkova) • Exchange of low amount of mechanical energy with the environment (Elia) • Electromagnetic fields (will see in the following)

9. Water • Gasesare fully non coherent systems • Liquids are systems where electron clouds are coherent • Solids are systems where nuclei, too, are coherent • Liquid water is peculiar, since the coherent oscillation connects two electronic configurations that have extreme features: • The ground configuration where all electrons are tightly bound (the ionization potential is 12.60 eV, corresponding to soft X-rays and to an excitation temperature of 145.000 °C !) 2) The excited configuration has an energy E=12.06 eV, only 0.54 eV below the ionization threshold. So for each molecule there is an almost free electron!

10.           Ө Ө Ө Ө Ө Ө Ө Ө Ө Ө Ө Ө Let’s have a look on the surface of solutes in water, or, what is the same on a wet surface. Negatively charged surface Positively charged surface

11. The general theory of the Van der Waals Forces (1961) • The basic idea of the theory is that the interactions between non-polar bodies is considered to take place through a fluctuating electro magnetic field. • These fluctuations are all the spectral components which have wavelengths large compared to the atomic dimensions. • All the properties of these long wavelength fluctuations, are completely specified through the complex dielectric permeability of the body. • The only limitation is that all the characteristic dimensions of the bodies must be large compared to the inter-atomic distances. Thus it applies to the macromolecules involved in the biological reactions.

12. l Forces between two bodies separated by a medium depend on the dielectric constant of 1, 2of the two bodies and 3 of the medium which fills the gap • characterize the absorption spectrum of the body d < l l~ 1-2 mm 1 2 d

13. Suppose that both bodies are sufficiently rarefied. From the point of view of macroscopic electrodynamics this means that their dielectric permeability are close to 1. We obtain the classical London formula (1930)

14. Attraction and repulsion depend on the medium which fills the gap It has to be noted that if the two bodies differ and the medium between them is water the interaction can be either an attraction or a repulsion: Ifandhave opposite sign then F < 0 and the bodies will repel each other. Ifandhave the same sign then F > 0 and the bodies will attract for “large” separation, the forces are determined by the electrostatic values of the dielectric constants.

15. Two atoms in water (Pitaevskii, 1959) • Weak solution of N1 and N2 atoms in the same solvent • Gap filled with pure water • For small concentrations the dielectric permeabilities ε1 and ε2 differ little from that of pure solventε3= ε This force corresponds to an interaction energy of the dissolved atoms equal to:

16. Dielectric properties of water We see that when the dissolved molecules interact strongly with the solvent the interaction forces between them are no longer determined by their polarizability but depend on the dielectric constant of the solvent ! experimental value * large distances non interacting dipoles Static dielectric constant coherent domains with respect to the wavelength of the em fluctuation *

17. Aqueous solutions used by Prof. Konovalov ‘s group have typical absorption line in their spectrum in the range of 200-600 nm. Hence, whenever the average distance among particles exceed such a length the following formula holds Energy is decreased by the formation of aggregates of coherent water having a higher static dielectric constant (Konovalov nanoaggregates) The magnetic field may protect the pile-up of the energy aligning the magnetic dipoles associated to the CDs thus stabilizing the aggregates.

18. Average distance less than l 200/400 nm depending on the substances Average distance greater than l 200/400 nm depending on the substances

19. The observed stable nano objects have a size of hundreds of nanometers which is in the same range of the wavelength characteristic of the spectrum of the solute. We suggest that whenever the dilution exceed a certain threshold where the average distance among solutes d ≫ l water Coherent Domains gather to form a mesoscopic region in order to decrease the free energy of the system. Stable water cluster may have a permanent electric charge (ζpotential) due to the quasi-free electrons at the border of the CDs. In bulk water such a feature cannot be observed because the lifetime of a CD is too short (10-15 sec)

20. We are talking about the arrangement of extended structures formed by the water coherent domains and the solutes. It is also possible that their collective vibrations could become coherent due to the principle of minimization of energy, this implies that water shift its oscillation frequency or (what is the same) its energy gap. Experimental hints: Blu shift of the IR spectrum of EZ water aquaphotomics

21. short distances * Water permittivity Hic sunt leones ! (here are the lions!) * with respect to the wavelength of the em fluctuation

22. A film of water on the surface of a solid body (EZ water) The chemical potential of the film per unit volume of the liquid is: For “large” thickness is proportional to R-4 with a coefficient depending on the electrostatic dielectric constants of the film and of the solid surface The function may change sign and be non-monotonic according to the sign of the difference

23. Permittivity vs frequency at 25°C for Nafion 117 Open the way for a theory for EZ water The collective vibration of dangling charges (SO3- sulfonic groups) of the surface and of the coherent water molecules could become coherent (blue shift) in order to further reduce the energy of the system water + Nafion

24. Dielectric constant 160 Dielectric constant 12 Nafion Non coherent molecules can enter into the Nafion structure. After a threshold of hydration they are attracted toward the surface Nafion acts as a phase separator Nafion EZ water

25. The effect of weak magnetic field on hydration of molecules

26. Phenylalanine Exposure to a static magnetic field 1 Gauss – 30 minutes FTIR spectra of aqueous solution of L-phe

27. pKa1 = 2.88± 0.03 MAGNETIC FIELDpKa1 = 3.31± 0.04 D1 =+0.43 The exposure of L-Phe to the magnetic field has an effect similar to the exposure to NIR radiation, which is known to cause significant changes in the hydration properties of such molecules. pKa2= 9.51±0.04 MAGNETIC FIELD pKa2= 9.41±0.04 D2=-0.1

28. H2O modifications aggregation pKa shift

29. The unusual property of EDTA is its ability to chelate or complex metal ions in 1:1 metal-to-EDTA complexes Classic form (H4y) EDTA Cr-EDTA

30. Following the formation of the complex via the UV-vis spectroscopy Two cuvettes C1 and C2. To the C2 cuvette have been applied two permanent, rare earth oxides, magnets having dimensions 52 x 13x 7 mm. The magnitude of the field is 2800±100 Gauss inside the cuvette. Absorbance at l = 540.0 nm of the EDTA-Cr(III) complex. Kinetic of formation of EDTA-Cr (III) complex: difference in the absorbance of exposed – not exposed samples.

31. Kinetic data, available in the literature, show that the rate constant for the reaction is accelerated with increasing the EDTA: • concentration, • pH, • temperature, • decreasing ionic strength and dielectric constant of the reaction medium • These results point towards an associative mechanism supported by the decrease of enthalpy and a large negative entropy for substitution of water by ligand compared to water exchange.

32. Water exchange Substitution of water by a ligand The much higher entropy gain of the reaction implies a larger scale ordering realized in the construction of the complex The magnetic field increases the kinetic constant affectingthe ordered structures of water molecules surrounding the hydrophobic chains. It increases the fraction of non coherent molecules available for the substitution of water by a ligand. The energy of the system water + solute is decreased.

33. Other experimental reports • Very High field: 10T • Refraction index increases of 0.1% (Hosoda et al.- J. of Phys Cem A, 2004, 108, 1461) • High field: 6T • Modifications when O2 is dissolved: Raman bands, contact angle, electrolytic potential (Otsuka and Ozeki – J. of Phys Chem B Lett 2006,110,1509-1512) • Low field: 45-65 mT • Vaporization enthalpy increases • Viscosity increases • Surface tension increases (Toledo et al. – J. of Mol Struct 2008, 888, 409-425)

34. Energy/matter exchanges in aqueous systems • The spontaneous evolution of the system is influenced by the environment (temperature, energy exchange, magnetic field). • In general it can be said that a system doesn’t reach the thermodynamic equilibrium unless the system is isolated. This principle is valid not only for the living matter but also for the inanimate one. • These considerations have been the basis of the experimental work of an Italian chemist, Giorgio Piccardi, in the ‘50s.

35. we suggest that water is the medium in which these exchanges at very low energy occur.

36. Thank you for your attention