Water Conference- De Ninno
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Transcript of Water Conference- De Ninno
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Antonella De NinnoCentro Ricerche ENEA Frascati Roma (Italy)
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Water Gases are 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 connectstwo electronic configurations that have extreme features:
1) The ground configuration where all electrons are tightly bound (the ionization potential is 12.60 eV, corresponding to soft X-rays andto 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 analmost free electron!
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The QED reveals us the dynamicalorigin of these clusters
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In liquid water two phases exist.
The interplay between the electrodynamic attraction andthermal disruption produces a continuous crossover ofmolecules between the two regimes.
The QED theory foresees a dynamical distribution
between the two phases F c, F nc of coherent and non-coherent molecules depending on the temperature:
( ) ( ) 1c nc F T F T
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How can we observe experimentallythe two phases in liquid water at roomtemperature and pressure ?
Measuring the energy differences between the two populations
via FT-IR spectroscopy we can measure the energydifference between the more correlated and the lesscorrelated kind of molecules and compare the result with theamount calculated by QED
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IR spectrum of liquid water
- 0 . 1
0 . 9
0
0 . 2
0 . 4
0 . 6
0 . 8
4 0 0 0 1 0 0 02 0 0 03 0 0 0
A b s
W a v e n u m b e r [ c m - 1 ]
OH stretchingvibration
Bending modeof the isolated
molecule
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0
7
2
4
6
4000 280030003500
Abs
Wavenumber[cm-1]
Experimental spectrum of waterT=25C
intermediateMolecules having a strongcorrelation with the
environment coherent
Monomers and/ordimers
non-coherent
ENERGY
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Comparison of the gas, liquid and solid spectra of the sameamount of water. From Martin Chaplin: Water Structure andScience web page http://www.lsbu.ac.uk/water/vibrat.html
http://www.lsbu.ac.uk/water/vibrat.htmlhttp://www.lsbu.ac.uk/water/vibrat.html -
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Such a system will also exhibit a Van't Hoff behaviour :
1. we can observe experimentally that our system (liquid water)
exhibits an equilibrium point upon changing the temperature, infact exists a point in the IR spectrum where the absorption isalways the same
0
0
ln
ln
eq
eq
G G RT K
G RT K
0 ln eq H T S RT K
Equilibrium constant can be used to evaluate thermodynamic parameters
3. we know from thermodynamics that at equilibrium the variation of the
Gibbsenergy, i.e., the maximum amount of useful work from a reaction is equalto 0
2. this suggests the existence of an equilibrium between two components
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Which components are the at equilibrium ?
0
7
2
4
6
4 0 0 0 2 8 0 03 0 0 03 5 0 0
A b s
W a v e n u m b e r [ c m - 1 ]
ENERGY
T1=30 C
T2=40C
T3=60C
Molecules having a strongcorrelation with theenvironment coherent
Monomers and/or dimers+ intermediate
non-coherent
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-0,3
-0,2
-0,1
0
0,1
0,2
0,3
0,4
2 ,9E-03 3 ,0E-03 3 ,1E-03 3 ,2E-03 3 ,3E-03 3 ,4E-03
1/T (K-1)
L n ( I 1
/ I 2
)
A plot of K eq vs. 1/T should be a straight line with
0
0
H slope RT S intercept R
Here the equilibrium constant is the ratio between the peak of thecoherent and non-coherent + intermediate populations
1
2
ln( ) I E
c I KT
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Vant Hoff plot
Experimental (T=300K)
Calculated (T=0)0.17 0.05 E eV 0.127 0.028 E eV
N.B. At T 0 actually, the boundaries are not sharp because of thethermal collisions and the energy gap is decreased.
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In such a picture, even the so called intermediate population could
find a rationale:the measured spectrum emerges from a dipole-dipoletransition between two specific quantum states
the intermediate peak is naturally assigned to the transitions where theinitial state is in the coherent fraction and the final state is in the non-coherent fraction and vice versa.(The average life time of the coherent state is ~ 410 -15 sec which isabout 2 times the vibration transition time scale)
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1. Is the dynamical distribution of the twophases only function of the temperature?
2. Is it affected by the interaction with the
environment?3. Can one phase be selectively stabilized?
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0,5
0,6
0,70,8
0,9
1
1,1
1,2
1,3
1,4
1,5
-1 0 1 2 3 4 5 6
Mol
A . U .
Coherent
Non-coherent
Is the dynamical distribution of the two phasesonly function of the temperature?
No, it also depends onthe concentration of solutes
NaCl solution
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Water near hydrophilic surfaces
Do the interaction with the environment affectthe distribution of the two phases ?
Yes, the quality of the surfacemodifies the percentage of thecoherent phase
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Peakposition
Area %
Coherent bulk water 3205 58Coherent EZ water
3292 76Intermediate bulk 3361 37Intermediate EZ 3494 4Non-coherent bulk
3526 5Non-coherent EZ 3610 20
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Egap decreased
t =1/ E gap increased
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EZ (interfacial) Bulk
Water is a heterogeneou s (at least a two -ph ase) sy stem inwh ich ch arge separat ion o ccurs be tween tw o ph ases :
low entrop y (organized) in terfacial and less organized bulk.
Up to 150 mv
+ N e g a
t i v e
l y c
h a r g e
d s u r f a c e
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How ever, we are dealing here with f ixed c harges
Negatively charged surface
Positively charged surface
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L ike ch arg es repel each oth er, b ut as th ey areco valent ly f ix ed to a m atr ix ,they a ll canno t bu t v ib rate
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Their co l lec t ive v ibra t ion co uld b eco m eco heren t d ue to th e p r inc ip le o f m in im izat ion
of energy
Interactions with the environment, inthis case the interaction with thesurface just acts like external trigger.Water appears to contain in itself theinformations.This may explain why the biologicmessage is NOT deterministic.
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Can one phase be selectively stabilized?
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ll d i @ i
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t ll d i @ it
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Light Scattering on water
Light scattering gives informationabout the presence of large sizeaggregates into the liquid providedthat a certain number of hypothesisin support of the Mie scatteringtheory are verified
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antonella deninno@enea it
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The supra molecular arrangement ofliquid water depends on:
TemperatureSolutes
Interfaces
We have observed the formation of stable structures ongoingafter the removal of the perturbation. This suggests the
formation of a stable far from- equilibrium state achieved troughthe dissipation of energy subtracted to the environment.
Electromagnetic signals
Concentration(thank to Prof. Konovalov for discussion)
antonella deninno@enea it
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pH
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The electric charge ranges from +1 in the fully protonated form to -2 according to the speciation scheme.
Glutamic acid speciation schemepH
pH=1.5 pH=11.8
When submitted to a weakELF/static electromagnetic fieldthe glutamic acid loses a proton
antonella deninno@enea it
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Phenylalanine
@
We have observed that the exposure to a weakmagnetic field of an aqueous solution of L-Phe inducesa measurable shift in the acid base equilibrium.
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Phenylalanine
Exposure to a static magnetic field 1 Gauss 30 minutes
@
The exposure of L-Phe to the magnetic field has an effectsimilar to the exposure to NIR radiation, which is known tocause significant changes in the hydration properties of suchmolecules.
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We suggest that:
the magnetic field acts as a chaotrope (disorder maker) agent,presumably acting upon the water supra-molecular structure. Amajor degree of aggregation between two amino acids isallowed whenever this layer is decreased by a magneticfield.
the size and the hydrophobicity of the R group of the aminoacids are responsible for the magnitude of the effect.
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logc0-10
EMF chaotrope effect
M o n
t a g n
i e r e
f f e c t
E M F e m
i s s
i o n
E f f e
c t o n m
M t
o M
s o l u
t i o n s
MF
EMF cosmotrope effect
It helps to formstructures?
???
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1. Is the dynamical distribution of the two phases onlyfunction of the temperature?
2. Do the interaction with the environment affect thedistribution of the two phases ?
3. Can one phase be selectively stabilized?
The supra molecular structure of liquid water is very sensitive to theenvironment including to the electromagnetic fields.
The appearance of stable structures that survive even to the phasetransition from liquid to solid state implies the existence of coherent space-time dissipative structures, capable of exchange energy and matter with theenvironment and attaining a different level of organisation.
Different kinds of water are then possibleaccording to the information exchanged with theenvironment.
Liquid water has a structure suitable totransform those information in significance andtherefore in meaning.
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Thank you for your attention