Subpage of Morrison Fleischmann debate
Copied from sci.physics.fusion, original post: Comments on Fleischmann and Pons paper. by Douglas R.O. Morrison. Eventually published in Physics Letters A 185, 28 February, 1994, 498-502. (Britz Morr1994)
Received 10 June 1993; revised manuscript received 5 October 1993; accepted for publication 14 December 1993
Communicated by J.P. Vigier
Abstract
(from the journal)
Fleischmann and Pons have claimed to have performed a “simple” experiment and to have observed excess enthalpies larger than 1 kW/cm 3 of palladium. It is shown that in fact the system they use is exceedingly complicated, is under-instrumented and that they have ignored several important factors so that it is unclear whether or not they have observed any excess heat.
From the newsgroup post:
DM-93/3.
5th DRAFT – Scientific Comments Welcomed. 6 May 1993.
Comments on claims of excess enthalpy by Fleischmann and Pons using simple cells made to boil
Douglas R.O. Morrison.
M. Fleischmann and S. Pons [1] have published in Physics Letters A a communication entitled “Calorimetry of the Pd-D2O system: from simplicity via complications to simplicity”. There they claim evidence for the production of excess enthalpy of greater than one kW per cc of Palladium in a Pd-D2O system. They comment that this is comparable with the rates obtained in a fast breeder reactor. They note that the reproducibility is high. In this letter serious doubts are expressed about this claim and the methods used to derive it.
Abd: I have often rued the very strong claims sometimes made by Pons and Fleischmann. Power density figures can sound very impressive, but rely on assumptions that are not actual knowledge (and very high power for a very short time is essentially meaningless). Comparing the energy density with a “fast breeder reactor” is asking for trouble. Did they claim “high reproducibility.” Yes, with a caveat. The actual quote, my emphasis:
We also draw attention to some further important features: provided satisfactory electrode materials are used, the reproducibility of the experiments is high; following the boiling to dryness and the open-circuiting of the cells, the cells nevertheless remain at high temperature for prolonged periods of time
That’s a striking claim, and it is basically ignored by Morrison. This “remaining at high temperatures for prolonged periods of time” has only one known prosaic explanation, and it’s implausible, as we will see.
Essentially they perform electrolysis in a transparent test tube which is open so that the gases and vapour can escape freely. The cathode is a small rod of palladium of 0.2 cm diameter and 1.25 cm length giving a total volume of 0.039 cm3. There are three stages.
“Freely” is a bit misleading. There is a very narrow path for gases to leave. It is not a “test tube,” it is a Dewar vacuum flask, silvered at the top.
For the first stage a moderate current is used for electrolysis. It is noted that at short times the heat transfer coefficient decreases – this they ascribe to the heat of absorbtion of hydrogen ions in the lattice.
In the second stage the current densities are raised to increase the temperature above 50 C – this with D2O. Finally, in stage three, the cells are driven to boiling point. A complicated (non-linear regression) analysis [2] is employed and it is calculated that there is excess enthalpy generated in the lattice, the amount calculated increasing steeply with time (and temperature).
Current density is a calculated figure. What is actually done is to raise the current. Note 2 is to a much earlier paper. “In the lattice” is not a finding in the paper. “Increasing steeply with time” does not appear to be shown.
In the third stage the behaviour near and during boiling is observed using a video camera. From this video, the time for the cell to go from about half-empty to dry, is taken – more precisely the amount of liquid boiled off is estimated over the final 10 minutes before the test tube was declared dry. A new simple calculation is made in which the enthalpy input is calculated as (cell voltage – 1.54 V)(cell current) and the enthalpy output is taken as composed of two terms, the energy radiated and the heat resulting from the vapourization of the D2O remaining in the cell 600 seconds before it is dry (this latter term is dominant). It is this simple calculation that gives the highest values claimed, namely “the excess rate of energy production is about four times that of the enthalpy input” and that the excess specific rate is 3.7 kW per cc of Palladium.
Morrison is looking at the complications and not the simplicity, which was variation in time to boil-off. I have never particularly trusted the enthalpy calculations from boil-off experiments, because the cell conditions become chaotic.
There are several major problems with this calculation.
First is that the “cigarette lighter effect” has been forgotten. In the last century it was difficult to make reliable matches to light cigarettes. A reliable smokeless lighter was invented which consisted of a rod of palladium into which hydrogen had been introduced under pressure. This caused the lattice of the palladium to expand and thus stored energy. To light a cigarette, the top of the rod was uncovered; some hydrogen escaped releasing some of the stress and thus releasing energy which resulted in a small rise in temperature of the end of the rod. Palladium is a catalyst of hydrogen and oxygen which burn to give water plus energy.
The palladium now slightly heated, catalyzes the escaping hydrogen and the oxygen
of the air and the resulting heat of combustion which is mainly deposited on the surface of the rod, raises its temperature. This temperature rise releases more hydrogen which is catalyzed by the still more efficient hot palladium, and so on until the tip of the rod is so hot that the cigarette can be lit. The reliability of this system is high.
Morrison misses the elephant in this living room. That effect requires the presence of oxygen, and the conditions in the cell when the cathode is finally exposed (wet palladium does not catalyze recombination) are such that there is very little oxygen, but increasing amounts of water vapor. Has recombination been “forgotten”? (“The cigarette lighter effect” is merely a dramatic way to refer to recombination. When electrolysis stops, the palladium will start to deload, forcing the water vapor and any remaining oxygen out of the cell. There is at this point a large loading of deuterium. Further, this effect would show up with hydrogen and with “dead cells.” Morrison is a physicist trying to school chemists on basic chemistry.
In the simple calculation used for stage three, a significant effect is omitted, of the heat produced by the catalytized recombination of the hydrogen with the oxygen. The oxygen is released from the anode by electrolysis, and towards the end when the cell is about dry, from the air. There is no mention in Fleischmann and Pons’s paper of any attempt to measure the amount of oxygen, deuterium and water in the gases and vapours leaving the test tube.
They omitted it. Not easy to do, by the way, though this has been done by others. However, these are electrochemists, and they know the chemistry well. Morrison has no respect. Electrolysis does release oxygen, and there would be, in boil-off cells where the electrolyte level is allowed to decline, exposed palladium which would indeed catalyze recombination, very effectively, but for some time the parts of the cathode have been exposed. These complications are part of my distrust of the excess heat calculations, but the effect does not explain the experimental results.
I rather doubt that the Morrison critique received careful attention from reviewers.
In the Fleischmann and Pons paper, it is noted as a further demonstration result, that “following the boiling to dryness and the open-circuiting of the cells, the cells nevertheless remain at high temperature for prolonged periods of time (fig.11); furthermore the Kel-F supports of the electrodes at the base of the cells melt so that the local temperature must exceed 300 C.” This dramatic effect cannot be explained by Fleischmann and Pons as being due to electrolysis since there is no liquid and no electrolysis.
That’s correct. It is not from electrolysis.
However it is exactly what would be expected with the “cigarette lighter effect” where the hot palladium rod continues to catalyze the interaction of the hydrogen which is slowly escaping from the rod, with oxygen from the air.
The rod would be no hotter than boiling, unless recombination becomes significant. Morrison is inventing an explanation that doesn’t hold water. In the terminal boil-off phase, electrolysis can only supply a little oxygen, enough to burn what is currently generated, and at dryness, no more oxygen. Okay, if the cell cools, wouldn’t oxygen enter through the vent? But if the rod is hot and there is no electrolysis, deuterium is being rapidly evolved. That cell will outgas for days. No. oxygen will not be sucked in, and these chemists know that.
It might be expected that this effect would occur also with normal water, H2O, being used instead of heavy water, D2O, but no description is given in the paper of any results of tests of the stage three boiling using normal water,H2O.
They did not describe everything. However, they did work with H20, see page 8.
An interesting confirmation of this using electrochemistry was reported by Kreysa, Marx and Plieth [3]. They write “We have to report here that as we removed the deuterium-loaded palladium sheet from the cell and laid it on the table it did burn a scald into the table. One can still argue that this was due to deuterium fusion. Therefore we loaded the palladium sheet cathodically with hydrogen using an electrolyte containing only normal water (no enriched heavy water) and laid it on to a piece of wood where it also burnt a scald.” They say it releases 147.3 kJ per mole D. “The principle of flameless catalytic combustion of hydrogen” – the official name of the ‘cigarette lighter effect’ – “is used in catalytic hydrogen burners (D. Behrens (ed) Waserstoffetechnologie – Perspektiven fur Forschung und Entwicklung, Dechema, Frankfurt/M 1986).” To be more quantitative they laid a hydrogen-loaded
sheet of palladium on to glass rods and “measured, after an incubation time of 15 s, a temperature rise of the palladium from 20 to 418 degres within 74 seconds.” The 15 second delay is the time during which the gradual escape of hydrogen releases a small amount of energy from the lattice, thus heating the palladium sufficiently for it to become an efficient catalyst. They estimate a heat flow of 35.9 W and a heat flow density of 179.6 W/cm3″.
This is really outrageous. Kreysa et al pulled that cathode out of the cell, so it was fully exposed to air. This is well-known, that a palladium cathode exposed to air will get very hot as it evolves hydrogen or deuterium, which will burn at the surface, and as it gets hotter, more hydrogen is evolved, etc. Morrison set this up to seem plausible by his misleading statement that the cell was open, which is technically true but not the whole story.
It may be noted that Fleischmann and Pons used an exceedingly small piece of palladium, 0.04 cm3, which works well as a catalyst, but which means that after catalyzing a larger volume of heavy water, the power calculated is apparently larger than with Kreysa et al. because the volume of palladium is so small. Should Drs. Fleischmann and Pons wish to test their previous conclusions [1], it would be interesting if they were to describe experiments where they repeated their published experiment but with a substantially larger amount of palladium and a relatively small volume of D2O.
Meaningless. Pons and Fleischmann had strong reasons for scaling down. The issue is the quantity of hydrogen/deuterium in the palladium, not how much has been “catalyzed,” which is incorrect here. This is electrolysis, not catalysis (recombination is catalysis.).
To see if that error made it into the journal, I compared. The newsgroup copy is radically different from the journal copy, so I’m terminating this analysis and will redo this page. I’ve been assuming that they were mostly the same, because of how others have treated this. Dangerous assumption, I’m learning that some are not careful.
Secondly, there is the assumption that ALL the liquid present in the tube 600 seconds before dryness, was boiled off. That is none of it was carried out as a liquid, from the test tube. Now the video shows that there is highly turbulent motion. And as Kreysa et al. [3] showed, 74 seconds after the palladium becomes dry, temperatures of a few hundred degrees can be reached. Thus it is reasonable to expect that with such a chaotic system, some fraction of the liquid is blown out of the test tube as liquid and therefore should not be counted. The existence of such a fraction is omitted from the simple Fleischmann and Pons calculation. And no attempt to measure this fraction is described.
Thirdly, the input enthalpy is taken as the current multiplied by the (cell voltage – 1.54V). It is not explained how these quantities are measured. This is crucial as when the cell is boiling vigorously, the impedance must be fluctuating strongly. Thus the current will have both an AC and a DC component. If only the DC component were measured, then the input enthalpy would be underestimated. A detailed description of the current and voltage measuring systems showing their fast response characters is needed, but is not presented.
Since these three important aspects of the experiment have been omitted, it is not possible to say whether or not excess enthalpy has been observed in the last 600 seconds to dryness (stage three).
There are two important problems with stage two.
Firstly, a complicated non-linear regression analysis is employed to allow a claim of excess enthalpy to be made. This method of Fleischmann and Pons [2] has been carefully studied by Wilson et al. [4] who state that “they significantly over-estimate the excess heat…….an additional significant overestimate of excess energy occurs when the calibration is made above 60 C”. Now stage two is mainly above 50 C and rising to 100 C. Further Wilson et al. write “Because of the paucity of experimental details in their publications, it has been difficult to determine quantitatively, the effect of calibration errors.” A reply by Pons and Fleischmann [5] did not address the main questions posed by Wilson et al.
Secondly, it may be noted in fig. 8 of ref 1, that the cell voltage rises as the temperature rises and that as 100 C is approached, the voltage rises more and more steeply. Experience by the GE group [6] was that in operating similar open cells over many hours, they also noticed a rise in cell voltage with time. They attributed this effect as being due to some of the escaping gases carrying some Lithium with them. As the level of the electrolyte is maintained by adding fresh D2O (but not any lithium salt), the concentration of lithium in the electrolyte decreases with time and the voltage rises. This was proved by atomic absorption analysis, that the cell resistance had risen (causing higher voltage due to the constant current mode operation) due to loss of lithium which was caused by sputtering of electrolyte droplets up the gas outlet tube. This may be considered confirmation that even at moderate temperatures, the outlet stream contains liquids as well as gases as discussed for stage three when the temperature was much higher and the boiling much more vigorous. It may be concluded that claims of excess enthalpy in stage two have not been established.
The overall conclusion is that many important factors have been neglected so that it has not been established that excess enthalpy was observed.
The experiment and some of the calculations have been described as “simple”. This is incorrect – the process involving chaotic motion, is complex and many calibrations and corrections are needed. The calculations have been made to appear simple by incorrectly ignoring important factors. It would have been better to describe the experiments as “poor” rather than “simple”. A true “simple” experiment is one where corrections and calibrations can be reduced to a minimum. This can be achieved in calorimetry by using a closed cell and by enclosing the cell in a series (eg three) baths which are each kept at constant temperature. The cell is kept at a higher temperature than the innermost bath so that if any excess enthalpy is produced, the heating of this bath can be reduced thus measuring simply the excess. Since this is a null measurement system, there is little need for complicated corrections. It is to be regretted that in the nine and a half years (the last four years well-funded) that Fleischmann and Pons say they have been working on this [7], that they have employed such a simplistic open-cell system.
It is a pleasure to acknowledge the help of many friends, in particular D. Britz, F. Close, T. Droege, R. Garwin, and S.E. Jones.
[Links added where available.]
[1]. M.Fleischmann and S. Pons, Phys. Lett. A 176 (1993) 1. [Britz Flei1993 and see our study page]
- [2]. M. Fleischmann and S. Pons, M.W. Anderson, L.J. Li, and M. Hawkins,
J. Electroanal. Chem. 287 (1990) 293. [lenr-canr copy] - [3]. G. Kreysa, G. Marx, and W. Plieth, J. Electroanal. Chem. 268(1989) 659. [Britz Krey1989]
- [4]. R.H. Wilson, J.W. Bray, P.G. Kosky, H.B. Vakil, and F.G. Will,
J. Electroanal. Chem. 332(1992) 1. [Britz Wils1992] - [5]. M. Fleischmann and S. Pons, J. Electroanal. Chem. 332(1992)33. [Britz Flei1992]
- [6]. General Electric group of ref. 4. priv. comm.
- [7]. Press release, University of Utah, 23 March 1989.
Notes
Can current fluctuations account for the excess heat claims of Fleischmann and Pons?