Protons and the Floating Water Bridge11th International Conference on the Physics, Chemistry and Biology of Water

Elmar C. Fuchs

High Voltage and Water

High Voltage and WaterHigh Voltage and Water

Sir William George Armstrong, 1st Baron Armstrong * November 26, 1810 † December 27, 1900

Armstrong, William George, "Electrical Phenomena", in: THE ELECTRICAL ENGINEER, Feb 10 (1893) p154-155

Electrohydrodynamic liquid bridge

Bridge Formation

Visualisation:Photron SA1 High

Speed Camera (B/W). Slow Motion

Factor 120.

slow motion

Visualisation:Panasonic Digital

Camcorder,real time.

Bridge Expansionreal time

Thermography

Visualisation: Equus 110L (IRCAM)

338 frames / s

bright: ~40°C

High Speed Thermography

Visualisation: Equus 110L (IRCAM); bright: ~40°C

Current simulation

Electric field simulationElectric displacement

Infrared Emissionwater emission 47°Cwater bridge emission

water emission 37°C

CO2 absorptionH2O vapor absorption

0

2400 2200 2000 1800 1600 1400 1200 1000 800

norm

. em

issi

on [

arb.

uni

ts]

wavenumber [cm]-1

5µm3µm = 3333 cm -1

12µm8µm

0

2400 2200 2000 1800 1600 1400 1200 1000 800

norm

. em

issi

on [

arb.

uni

ts]

wavenumber [cm]-1

Infrared Emissionwater emission 47°Cwater bridge emission

water emission 37°C

CO2 absorptionH2O vapor absorption

thermographic camera 1

thermographic camera 2

thermographic camera 1 thermographic camera 2

Infrared Emission

3-5µm region is as bright as 47°C, 8-12µm region as bright as 37°C waterThere is an additional, non-thermic emission at shorter wavelengthsThis emission is interpreted as result from a protonic band transition

E.C. Fuchs, A. Cherukupally, A.H. Paulitsch-Fuchs, L.L.F. Agostinho, A.D. Wexler, J. Woisetschläger and F.T. Freund, Investigation of the Mid-Infrared Emission of a Floating Water Bridge, J. Phys. D: Appl. Phys. 45 (2012) 475401

Proton production, conduction and reduction

liquid flow gas flow ion flow

Measurement of the OH-vibration in an HDO moleculeDuration of vibration gives information about the H-bond network

Vibration stops faster in solid phase and last longer in liquid phase

hexagonal ice

liquid water

Ultrafast vibrational energy relaxation

300

400

500

600

700

OH

- st

retc

h vi

brat

iona

l life

time

/ fs

water bridge~ 25°C

ice

liquid water

ice 0°C

liquid water0°C

phase transition

Proton mobility

S( )water bridgewater in Al cylinder

inte

nsity

/ 10

a.u

.4

/ 10 µeV3

-10 -8 -6 -4 -2 0

3.0

2.5

2.0

1.5

1.0

0.5

0

"Quasi-elastic neutron scattering" - QENS

QENS data evaluation

/ 10 µeV3

800

-5 -4 -3 -2 -1 0

400inte

nsi

ty /

a.u

.

0

Q = 0.655871Å-1

Instrument resolution ( function, V)

S(Q, )

Lorentzian

Data pointFit: Lorentzian + function (V)

(Q)=DQ²

1+DQ²0

HWHM of the LorentzianRandom jump diffusion model:

Diffusion coefficient

/ µE

. . . .Q² / Å-

Water i Al li derWater ridge

Water °C si ulatio ith utliple s atteri g orre tio

Water ridge fit

Corre ted ater ridge ur e% o fide e i ter al

Water i Al li der fit

°C si ulatio% o fide e i ter al

Dwb= (26±10)·10-5 cm s-1Dw,50°C= 4.0 ·10-5 cm s-1

0,wb=(0.55±0.08) ps0,w,50°C= 1.00 ps

Proton mobility

Method to al ulate proto o ility µH / -7 m² V- s-

Stokes – Ei stei Diffusio oeffi ie t fro this easure e t

Te perature depe de t o E-field .

Ostrou o , Stuetzer a d Féli i .Féli i i pro ed ethod .

.

Charge mobility for EHD purposes has been reported "anomalously high"Stokes - Einstein relation allows to calculate proton mobility in the bridge

E. C. Fuchs, B. Bitschnau, A. D. Wexler, J. Woisetschläger, F. Freund, “A Quasi-Elastic Neutron Scattering Study of the Dynamics of Electrically Constrained Water,” J. Phys. Chem. 2015, 119 (52), pp 15892–15900

D=µqkBT

q

Proton jumps< l a > = D

l (water, 50°C) ~ 1.6 Å nearest neighbor interaction (Grotthuss)

l (wb, 50°C) ~ 3.0 Å next to nearest neighbor interaction

Quasi - free protonsQuantum mechanical interpretation of the Grotthus mechanism"Proton channel": proton conduction band across 3 water molecules"Band structure" is normally associated with a solid materialPhase is deteremined by the intermolecular bond strengths (H-bond)

Proton production, conduction and reduction

liquid flow gas flow ion flow

M. Sammer, A.D. Wexler, P. Kuntke, H. Wiltsche, N. Stanulewicz, E. Lankmayr, J. Woisetschläger, E.C. Fuchs, J. Phys. D: Appl. Phys 48 (2015) 415501

EIS of waterE peri e tal data

Fitted data

C

Raq

. E+

. E+

. E+

. E+

. E+

. E+

. E+-I

) /

. E+ . E+ . E+ . E+ . E+ . E+ . E+Re ) /

100 Hz - 107 Hz

E.C. Fuchs, M. Sammer, A.D. Wexler, P. Kuntke, J. Woisetschläger, J. Phys. D: Appl. Phys. 49 (2016) 125502

EIS of anolyte and catholyte

R1A

R2A

C1A

C2A

R1C

R2C

C1C

L

E peri e tal data a ol teFitted data a ol teE peri e tal data athol teFitted data athol te

. E+. E+ . E+ . E+ . E+ . E+ . E+ . E+

. E+

. E+

. E+

. E+

. E+

. E+

-I)

/

Re ) /

E.C. Fuchs, M. Sammer, A.D. Wexler, P. Kuntke, J. Woisetschläger, J. Phys. D: Appl. Phys. 49 (2016) 125502

Anolyte

A ol te, easure e t

A ol te, easure e t

A ol te, easure e t

-I)

/

-I)

/

-I)

/

Re ) / Re ) / Re )

H+ + e- 1/2 H2

Reduction destroys charge carriers, the impedance increases with each measurement

Catholyte

Cathol te, easure e t

Cathol te, easure e t

Cathol te, easure e t

-I)

/

Re ) /

2OH- 1/2 O2 + H2O +2e-

OH- are not present at pH 5.5, so the oxidation "frees" previously occupied protons, thus the impedance decreases with each measurement

Charged water

H2.00000000045O+ H2O H1.9999999986O

~5mC/L ~5mC/L

Summary

An aqueous electrohydrodynamic floating bridge (a.k.a. "floating water bridge" -FWB) resembles a protonic resistorThe protonic charge flow heats up the water bridge and can be visualizedProtons are generated by electrolysis in the anolyte and are neutralized in the catholyteThe water in an FWB is in an electrically excited state with increased H-bond strength that lies inside the "no man's land" of the phase transition between ice and liquidIn this excited state protons reveal an increased mobility and travel through "proton channels"If the a FWB is stopped abruptly, excess protonic and aterprotonic charge remain in the water (~5mC/L)

Thank you for your attention.

Protons and the Floating Water BridgeElmar C. Fuchs1

With cordial gratitude to those who made this research possible and contributed to it: J. Woisetschläger2, A.D. Wexler1, H. Bakker10, F. Freund3, B. Bitschnau4, J. Teixeira5, A. Soper7, E. Del Giudice8, G. Vitiello9, B. Beuneu5, K. Gatterer4, H. Eisenkölbl4, G. Holler6, J. Tuinstra1, C. Buisman1, the companies in the AWP theme, and many more.

1. Wetsus, Centre of Excellence for Sustainable Water Technology, Agora 1, 8900 CC Leeuwarden, The Netherlands2. Graz University of Technology, Institute for Thermal Turbomachinery and Machine Dynamics, Austria3. NASA Ames Research Center, Moffett Field, Mountain View, CA, USA4. Graz University of Technology, Institute of Physical and Theoretical Chemistry, Austria 5. Laboratoire Léon Brillouin, Centre d'Études Nucléaires de Saclay, 91191 Gif-sur-Yvette Cedex, France6. Graz University of Technology, Institute of Electrical Measurement and Measurement Signal Processing, Austria7. ISIS Facility, STFC Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, Oxon, OX11 0QX, United Kingdon8. Istituto Nazionale di Fisica Nucleare, Sezione di Milano, Milano - 20133 Italy9. Dipartimento di Matematica e Informatica and INFN, Universitá di Salerno, Fisciano (SA) - 84084 Italy10. FOM Institute AMOLF, Amsterdam, The Netherlands

http://www.phdpositionswetsus.eu/