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260) Facts versus interpretations

Ludwik Kowalski (9/25/05)
Department of Mathematical Sciences
Montclair State University, Upper Montclair, NJ, 07043

As mentioned before, I belong to the International Society of Condense Matter Nuclear Science (ISCMNS). That society has a restricted discussion list, called CMNS, for its members. In units #252 I wrote about an anticipated experiment. The setup has already been assembled at ETI in Austin (by Scott Little and George Luce); I am going to join them tomorrow. Various aspects of that experiment were discussed in units #253, #255, #256, #258 and #259. What I want to show here is the continuation of the discussion that was described in unit #259.

Voices from the CMNS list:
1) Responding to ZZ, YY wrote:
“Yes, I agree that the energy needed for vaporization is the same. However the source of that energy could be other than purely heat applied. Some of that energy could be derived from dielectric insertion. It is also an energy source. There is energy released by insertion of a dielectric into a constant potential capacitor. That is: the 2267J/g can come in part from heat and part from other sources. The thing that must be kept in mind is that even if you created water vapor between capacitor plates, and find that it takes lest heat than you expect to vaporize it in the region between charged capacitor plates, it would take an addition amount of energy to remove it from that region.”

2) Responding to my message (shown at the end of unit #259) YY wrote:
“I think that you are focused on Fauvarque's recent work. The problem, is that he is assuming that the loss of weight is due to water being removed by evaporation. Could it just be that some water is leaving by droplets in the gas flow? The water surface of these things is very active and they did see droplets outside the beaker. I would want more care on that point before I would spend too much time on the possibilities that you are asking about altering the latent heat of vaporization. The same with Mizuno's gas levels of 80 times Faraday numbers - could some of it be CO2 from the electrolyte?”

3) My reply was:
“The first thing Fauvarque et al. did was to measure the latent heat of evaporation with the immersion heater (see Figure 2 in their paper). They measured L at several wattages, up to 600 W. In all cases the measured value was essentially 2260 J/g. Boiling is quite intense at 600 W; if droplets were ejected the value of L would be significantly smaller than the accepted value. This shows that both thermal and electric measurements were accurate. One may argue that droplets are more likely to be ejected when the current flows through an electrolyte, that when it flows through a wire. Oxygen and hydrogen bubbles might carry some invisible droplets, especially when the current is large. I do not know if ohmic heating at 600 W generates more invisible droplets than electrolytic heating at 250 W (at which significant excess heat was reported). What kind of control experiment would you (or others on the list) suggest to demonstrate absence of droplets? Rita permitting, I might be involved in another attempt to replicate the Mizuno-type experiment (next week in Texas). We would be happy to add control experiments designed to make conclusions more acceptable.”

4) YY responded:
“I would suggest that you consider the reflux calorimeter method (see my ICCF4 paper in the proceedings). Basically you put a condenser on top of the cell, and do flow calorimetry on the water flow of the cooling condenser with everything well insulated. You also can put a recombiner at the top of the condenser. The surface of an electrolytic system at several hundred watts can be very "frothy" and very fine droplets can be produced when the bubbles pop. Hydrogen gas in the bubbles "lift" more than just water vapor. I would be very cautious using water loss as a measure of heat. You might could check things by measuring the carbonates remaining in the solution. I would think that the droplets would remove some of the carbonates but evaporation would not. I have not proceeded that way, but it might be a good check.”

5) A message from WW (who did observe droplets):
“In the past I did a lot of experiments using a plasma electrolysis system (send to me by E. Mallove) with a condenser which was built on top of the electrolysis cell.(about 1-1.5 meter high). The condensate was collected in a flask. I used a W cathode and a platinum anode during the electrolysis of K2CO3.(in the beginning to carbon electrodes). The main purpose of this experiment was to look for changes in T 1/2 of radioactive elements. First I used radioactive Thallium 201. I put about 5 MBq of 201 Tl into the solution and started electrolysis with a low current. After a few hours the Thallium was adsorbed on the W electrode. I measured the gamma emission with a solid state detector. Then I increased the voltage to 70-80 V and plasma electrolysis started . Then the voltage was increased until 220V. During the experiment I could clearly see a drop in gamma emission from the solution. After electrolysis I noticed that a lot of the radioactivity could be found on the bottom of the reaction vessel, mainly in (WO2?) particles. I concluded that the change in geometry of the distribution of radioactivity caused the decrease in gamma counts. I did not persue further analysis of the particles. Further it was remarkable that about 10- 20% of the radioactivity was found in the condenser solution. I concluded then that droplets with radioactive solution went through the condenser into the condensate. My conclusion was that during my experiment about 10-20% of the solution was not evaporated but was transported as small droplets. This has to be taken into account if one wants to calculate the power balance of the cell. It is possible that during more intense plasma electrolysis at higher voltages,higher percentages of non evaporated solution can be expected.”

6) My comment on what YY wrote:
“a) While reading YY's paper I realized that he was also addressing the issue of the path #2 (ejection of liquid water from the electrolyte at the energy cost of less than 2267 J/g). The only difference between his version and my version is the mechanism of the second path. I had no idea what the mechanism might be; Dennis associated it with invisible droplets in the streams of bubbles of hydrogen and oxygen. Each of us is saying that excess heat in high voltage electrolysis, or at least part of that heat, might turn out to be apparent. As far as I know that potential source of error was not discussed by those who published reports on excess heat in Mizuno type cells. Is this a correct assessment? How can this be explained?

b) The way to eliminate the suggested source of error is worth taking seriously. It is probably too late to try D2's old approach in our next-week experiment. But it is something to consider, if the excess heat is observed.

c) The idea of paying attention to the concentration of the K2SO3 in the electrolyte is also attractive. The initial concentration is 20 grams per liter. After only two 5-min tests one is expected to loose about 100 cc of liquid water. Let me tentatively assume that 50% of that is removed in the form of droplets (producing a lot of apparent excess heat) . That would take away 1 gram of the salt. The concentration of the remaining electrolyte, in Fauvarque's experiment, would then change to 19 grams per liter. Such change is probably not very difficult to measure. Here is a suggestion for our next-week experiment. A sample of the initial electrolyte should be preserved in a bottle. The used electrolyte, for example after ten or twenty tests, should also be preserved. A comparison of concentrations seems to be worth making. Why was this not done before? Thanks for the suggestion, D2.
d) VV's contribution is extremely valuable. It shows how radioactive tracers can be used to perform very accurate measurements of the relative contribution of the path #2 identified by Dennis. The probability of the path #2 should increase with the voltage because the current (and the associated rates of generation of O2 and H2 bubbles) becomes larger. If that is true then the excess heat should also go up with volts, as reported by Fauvarque et al. But that would be an apparent excess heat.”

7) Responding to droplets mentioned by YY, VV wrote:
“(a) I do not know how he confirmed this. Ohmori confirmed it by placing paper towels around the cell, and weighing them after the run.
(b) No. The gas goes through a condenser and then a sample is sent through a mass spectrometer to measure composition.
See: <>.”

8) YY responded:
Thank you; I had not seen that paper. I am quite taken by his figure 10. This is quit comforting. The jump in output between 70 and 75 is about what I had noticed in many other CF type systems. In fact I now (since 95) run most all my "good" CF cells above 72 C and many right at boiling. I would say that although Mizuno runs similar electrodes (W,W/Th.... ). I normally run with sulfamic acid (yes, that is sulfamic not sulfuric) at higher current densities.

As an aside- mine glow blue instead of yellow/orange. See picture on my home page <>.

My work right now is going after the hydrogen stream. I am also trying to see if I can get some additional photo-dissociation within the cells. (Compare to work of using Rh ions to mimic photosynthesis and creating the ions in situ from the electrolysis by adding rare earth ions to the electrolyte). As I said in an earlier thread, recovering H for part of the "excess" energy makes the engineering breakeven easier since you only get about 30% of the heat back (for an electrical input loop)-if you are very good- because of Carnot, but you can get 60 to 90% back in the H stream via a fuel cell to use for input electrical energy. I hope to get some funding to be able to burn it "in" a Stirling engine. I have a small one right (about 1 Watt)now but it is hard to match to the high power levels. I have not yet been able to scale down these sparkly cells to levels below about 70 or so watts. It is much easier to get them to "work" at higher levels. You need the high current densities and if you scale it down you have to use a point and those just erode very quickly. Thanks for the info.

9)My message:
According to the 2005 paper of Mizuno et al., <> the temperature and pressure in the plasma region are extremely high (up to 9000K and 4000 atm. respectively). I am inclined to think that a sizable fraction of the liquid water lost during each test is vaporized near the cathode. And it is reasonable to thing that the fraction increases with the voltage. (Foe example from ~0% at 200 V to ~36% at 350 V.) That fraction would be "the abnormal" evaporation.

In the Sears and Zemansky's "University Physics" I see this statement : "as we approach the critical point [along the vaporization curve in the pT phase diagram] the differences in physical properties between the liquid and vapor phases become smaller and smaller. . . . THE HEAT OF VAPORIZATION ALSO BECOMES SMALLER AND SMALLER AS WE APPROACH THE CRITICAL POINT, AND IT TOO BECOMES ZERO AT THE CRITICAL POINT." I suppose that this statement was more than a speculation; it was probably based on some experimental evidence.

Thus associating abnormal evaporation with the lower than usual heat of vaporization is not at all silly. The implied assumption (made not only by Fauvarque et al.) -- that the average latent heat of vaporization is 2267 J/g -- might be not valid. Accepting this point of view one would conclude that the reported excess heat might be apparent. Thus we can list five competing qualitative explanations of experimental data:

a) Excess heat is real; it is due to nuclear reactions.
b) Excess heat is apparent, due to ejection of tiny droplets (experimentally observed by Peter van Noorden).
c) Excess heat is apparent, due to the lowering of the average heat of evaporation.
d) Excess heat is real but its origin remains to be identified.
e) Excess heat is apparent for a reason not connected with (b) and (c).

I would like to know how rapidly L decreases when T is going up. Unfortunately, the water vapor table I consulted does not have a column for L.”

9) I expected to hear from more of those who reported on reality of excess heat on the basis of the amount of water evaporated. Their contributions to the debate, if any, will be appended here. Please revisit.

9) XX responded:
“I don't think ‘c’ can be an explanation for the apparent excess heat results. I agree that the heat of vaporization does go to zero as you reach the critical point (where there is no distinction between liquid and gas, hence no such thing as vaporization anymore). But, as Miles told us, ‘L (change in enthalpy for vaporization) is a STATE function, hence it can only depend on the initial and final states-it is independent of path.’ Thus, the following two processes will require exactly the same energy input:

a) Evaporating 1 gram of water at 100C and 1 atm pressure (i.e. ordinary boiling).

b) Taking 1 gram of water at 100C and 1 atm pressure up to the critical point, evaporating it there for ‘free’, and then bringing the resulting vapor back down to 100C and 1 atm.

In our experiment, water at 100C and atmospheric pressure moves towards the cathode where it is somehow converted into vapor. The vapor bubbles rise up through the water and burst at the surface releasing water vapor that is essentially at 100C and atmospheric pressure. From an energetic viewpoint, I think we can therefore ignore the details of the vaporization process at the cathode.”

10) YY responded:
“You may also want to look at the fugacity of the water at the cathode. But it too is a state function. Just having done this types of items, I would first design the experiment to check b) first.”

11) My reply (not posted):
I agree with this, if what “evaporates” at much higher p and T consists of common H2O molecules. But the first law does not seem to be violated if the substance escaping from the liquid does not consist of H2O. The escaping matter might become H2.O, outside of the cell, at the expense of energy of some chemical reactions. I should have phrased the explanation (c) more carefully, as I did before. In any case; we are not discussing water as a fluid in a cyclically operating, and reversible, engine.

12) I expected to hear from more of those who reported on reality of excess heat on the basis of the amount of water evaporated. Their contributions to the debate, if any, will be appended here. Please revisit.

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