Protons and the electrical conduction in a Floating Water Bridge

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1 Protons and the electrical conduction in a Floating Water Bridge 9 th Conference on the Physics, Chemistry and Biology of Water Bulgaria, October 9 th, 2014 Elmar C. Fuchs combining scientific excellence with commercial relevance

2 High Voltage and Water

3 High Voltage and Water

Discovery Armstrong, William George, "Electrical Phenomena", in: THE ELECTRICAL ENGINEER, Feb 10 (1893) p154-155 Visualisation: Panasonic digital video camera, real time ".

4 Discovery Armstrong, William George, "Electrical Phenomena", in: THE ELECTRICAL ENGINEER, Feb 10 (1893) p Visualisation: Panasonic digital video camera, real time "...Amongst other experiments I hit upon a very remarkable one. Taking two wine-glasses filled to the brim with chemically pure water, I connected the two glasses by a cotton thread coiled up in one glass, and having its shorter end dipped into the other glass. On turning on the current, the coiled thread was rapidly drawn out of the glass containing it, and the whole thread deposited in the other, leaving, for a few seconds, a rope of water suspended between the lips of the two glasses...." Sir William George Armstrong, 1 st Baron Armstrong * November 26, 1810 December 27, 1900

5 Experimental Set-up 42 nf 6 cm V 500 kω 500MΩ + 15 kv I = 0,5 ma (const.) 0,000g 0,000g 0,500g -0,500g

6 Bridge Formation slow motion Visualisation: Photron SA1 High Speed Camera (B/W). Slow Motion Factor 120.

7 Visualisation: Panasonic Digital Camcorder, real time. Bridge Expansion

8 Macroscopic analysis Electric displacement (calculation)

Microscopic analysis Ultrafast vibrational energy

molecule Duration of vibration gives information about

water phase transition hexagonal ice ice 0 C Vibration

9 Microscopic analysis Ultrafast vibrational energy relaxation Measurement of the OH-vibration in an HDO molecule Duration of vibration gives information about the H-bond network liquid water 0 C liquid water liquid water phase transition hexagonal ice ice 0 C Vibration stops faster in solid phase and last longer in liquid phase ice

10 Microscopic analysis Ultrafast vibrational energy relaxation 700 liquid water 0 C liquid water The -OH vibrational relaxation time (T 1 ) is faster in the floating water bridge (~630±50 fs) than in bulk water (~740±40 fs), and slower than ice (384±16 fs) OH - stretch vibrational lifetime / fs water bridge ~ 25 C ice 0 C phase transition ice The thermalization dynamics following the vibrational relaxation are much slower in the water bridge (~1.5±0.4 ps) than in bulk HDO:D 2 O (~250±90 fs) The observed relaxation time of ~630±50 fs of the water bridge is not observed at any temperature for bulk water These results show that in the bridge water exists in a new state different from both liquid and solid.

11 Electrical conduction Electrical conduction in water normally involves electrolysis. Electrolysis entails: Gas production ph change Gas production is not observed during water bridge operation.

12 Electrical conduction Electrical conduction in water normally involves electrolysis. Electrolysis entails: Gas production ph change Gas production is not observed during water bridge operation. How much gas would actually be produced? Farady's law: n = (I t)/(z F) I = 400 µa, t = 30 min, z = 2 (number of electrons per mole gas) and F = C mol -1 At 25 C one mole of an ideal gas occupies L. If O 2 and H 2 are considered ideal gasses, their volumes amount to 91 and 183 µl If those gasses would form bubbles at the electrode, there should be 174 O 2 bubbles and 349 H 2 bubbles formed over 30 minutes assuming 1 mm as bubble diameter That would be one bubble every 10 and 5 seconds, respectively. Why don't we see them?

13 Visualisation: Panasonic Digital HD Camcorder, real time. Schlieren Visualisation Cuvettes & floating bridge

14 Hypothesis: Gas formation without bubbles e - e - H2 O2 Lemniscate flow Temperature gradient Gas is dissolving

15 In search of Hydrogen: Gas formation without bubbles intensity / µv Airtight dome flushed with N 2 GC analysis after 100 min of bridge operation Hydrogen presence confirmed Measured: 0.88mL Calculated: 0.84mL H 2 concentrates on top of the dome where the sample is extracted N 2 8 cm H 2 O kv time / ms

16 Electrical conduction Electrical conduction in water normally involves electrolysis. Electrolysis entails: Gas production ph change How large should the ph shift be? Electrode reactions: Anode: 2 H 2 O O H e - Cathode: 2 H 2 O 2e - + H OH - Farady's law: n = (I t)/(z F) I = 400 µa, t = 30 min, z = 2 (number of electrons per mole gas) and F = C mol -1 Theoretical ph: Anolyte: ph 2, Catholyte: ph 10 Measured ph: Anolyte: ph 5.5, Catholyte: ph 5 Where do the produced protons and hydroxyl ions go?

17 Thermography Visualisation: Equus 110L (IRCAM) 338 frames / s bright: ~40 C

18 High Speed Thermography Visualisation: Equus 110L (IRCAM); bright: ~40 C

The protons travel. 3µm = 3333 cm -1 5µm water bridge emission water emission 47 C water emission 37 C thermographic camera 1 thermographic camera 2 norm. emission [arb.

19 The protons travel. 3µm = 3333 cm -1 5µm water bridge emission water emission 47 C water emission 37 C thermographic camera 1 thermographic camera 2 norm. emission [arb. units] 8µm 12µm Visualisation: Equus 110L (IRCAM); bright: ~40 C 0 CO 2 absorption H 2 O vapor absorption wavenumber [cm] -1 There is an additional, non-thermic infrared emission from travelling protons These are the protons produced at the anode, and neutralized at the cathode. E.C. Fuchs, A. Cherukupally, A.H. Paulitsch-Fuchs, L.L.F. Agostinho, A.D. Wexler, J. Woisetschläger and F.T. Freund, J. Phys. D: Appl. Phys. 45 (2012)

20 Proton neutralization in catholyte Electrical conduction in water normally involves electrolysis. Electrolysis entails: Gas production ph change Electrode reactions: Anode: 2 H 2 O O H e - Cathode: 2 H 2 O 2e - + H OH - e - e - e - e - H2 O2 OH - H + + H + H Lemniscate flow Gas is dissolving H O 2 Protons are neutralized

21 Proton neutralization + 13 kv

22 Proton neutralization + 13 kv

23 With and without dye a + 13 kv + 13 kv d b H + e H + OH - H + OH - H + c f

24 Other ions ICP analysis of anloyte and catholyte Deionized water stored in a glass bottle dissolves ions from the glass The amount of dissolved CO 2 is an order of magnitude larger than the trace element concentration The amount of dissolved Pt is an order of magnitude smaller than the trace element concentration Carbon 0.6 Platinum µg / L 8 6 µg / L R A C µg / L R A C Na K Mg Ca Zn Pt Reference Anode Cathode LOQ

25 Other ions ICP analysis of anloyte and catholyte Reference - HCO 3 Contribution to the overall conductivity Na + K + Mg 2+ Ca 2+ Zn 2+ Pt 2+ H + OH - HCO 3 - Anode - HCO 3 Cathode - HCO 3 H + H + H + Metal ions: ~ 2% HCO 3- : ~ 10% Protons: ~ 88% calculated conductivity measured conductivity µs cm -1 µs cm -1 Reference 0.93 ± ± 0.08 Anolyte 1.18 ± ± 0.08 Catholyte 0.98 ± ± 0.08

26 Summary The electrical conduction in a floating water bridge is protonic Protons are produced by electrolysis at the anode, travel through the bridge and are neutralized at the cathode Because the current is very low (typically <1mA), the amounts of gasses produced is very small and difficult to detect Other ions are present, but their role in the conduction is negligible

27 Jakob Woisetschläger Friedemann Freund... Lukasz Piatkovski Martina Sammer Huib Bakker Adam D. Wexler Astrid H. Paulitsch-Fuchs Philipp Kuntke combining scientific excellence with commercial relevance

28 Protons and the electrical conduction in a floating water bridge Elmar C. Fuchs 1 With cordial gratitude to those who made this research possible and contributed to it: M. Sammer 1, J. Woisetschläger 2, A.D. Wexler 1, H. Bakker 10, L. Rothschild 3, F. Freund 3, B. Bitschnau 4, J. Teixeira 5, A. Soper 7, E. Del Giudice 8, G. Vitiello 9, B. Beuneu 5, K. Gatterer 4, H. Eisenkölbl 4, G. Holler 6, J. Tuinstra 1, C. Buisman 1, the companies in the AWP theme, and many more. 1. Wetsus, Centre of Excellence for Sustainable Water Technology, Agora 1, 8900 CC Leeuwarden, The Netherlands 2. Graz University of Technology, Institute for Thermal Turbomachinery and Machine Dynamics, Austria 3. NASA Ames Research Center, Moffett Field, Mountain View, CA, USA 4. Graz University of Technology, Institute of Physical and Theoretical Chemistry, Austria 5. Laboratoire Léon Brillouin, Centre d'études Nucléaires de Saclay, Gif-sur-Yvette Cedex, France 6. Graz University of Technology, Institute of Electrical Measurement and Measurement Signal Processing, Austria 7. ISIS Facility, STFC Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, Oxon, OX11 0QX, United Kingdon 8. Istituto Nazionale di Fisica Nucleare, Sezione di Milano, Milano Italy 9. Dipartimento di Matematica e Informatica and INFN, Universitá di Salerno, Fisciano (SA) Italy 10. FOM Institute AMOLF, Amsterdam, The Netherlands Thank you for your attention. combining scientific excellence with commercial relevance

A New State of Water. combining scientific excellence with commercial relevance. Elmar C. Fuchs

A New State of Water. combining scientific excellence with commercial relevance. Elmar C. Fuchs A New State of Water Elmar C. Fuchs Invited presentation at the 7 th Annual Conference on the Physics, Chemistry and Biology of Water Mount Snow, Vermont, USA October 20 th, 2012 combining scientific excellence