Doctoral Thesis Concludes Pons-Fleischmann Heat Effect Artifact of Chemical Reaction

Thanks to Curbana for making me aware of this 2012 doctoral thesis which I had not seen before, written by University of Colorado doctoral candidate in electrical engineering Olga Dmitriyeva titled “Mechanism of heat generation from loading gaseous hydrogen isotopes into palladium nanoparticles” which is an attempt to understand the underlying cause of the anomalous heat effect measured in palladium-deuterium reactions first made famous by Pons and Fleischmann in 1989.

Dmitriyeva states that her interest in this subject stemmed from the fact that there were claims by some researchers that the excess heat measured correlated with helium production (indicating a nuclear reaction) while other attempts were unsuccesful.

Without getting in to the details of the research, Dmitriyeva carried out which are described exhaustively in the thesis (see the link above), she concludes that the heat phenomenon can be explained as a result of an artefact caused by a chemical reaction.

Here is a summary from the introduction:

To prove the chemical nature of the observed phenomena I demonstrated that the reaction can be either exo- or endothermic based on the water isotope trapped in the material and the type of gas provided to the system. The H/D exchange was confirmed by RGA, NMR and FTIR analysis. I quantified the amount of energy that can be released due to the H/D exchange and proved that the heat generated during the experiments can be fully accounted for by this chemical reaction.

At the end of the dissertation in a section about future work, Dmitriyeva mentions the work that has been done in the field of nickel-hydrogen reactions and notes that her chemical reaction conclusion does not apply to nickel-hydrogen reactions. She writes:

[T]here is another large cluster of work that has been done with Ni and NiCu alloy materials and hydrogen, and for which H/D exchange
reaction does not provide an explanation. Hydrogen, as a reaction gas, does not satisfy the condition for the exothermic reaction described in Table 4. Hydrogen exposure would produce either no heat if the material is saturated with H2O, or the reaction would be endothermic if D2O 89 is trapped in the sample. I do not dismiss the chemical explanation to the excess heat observed in Ni-H systems, but the details of the reaction are unknown.

I am guessing that this will be considered a controversial study by many cold fusion enthusiasts, but I post it here because I think it’s relevant to the discussion, and the research seems to have been done in a thorough manner (I am not qualified to critique the experimental protocols used). I do find it interesting that Andrea Rossi, while giving credit to Pons and Fleischmann foropeningg a new field of study, seems to not to believe that their process was valid. He himself tried to replicate their effect without success in his early research, and recently made this comment:

What inspired me to begin, to be honest and sincere, has been the work of Prof Fleishmann and Prof Pons when it has been announced the first time. This is a merit they deserve, even if the electrolysis concept was, and still is, wrong. The electrolysis brings nowhere. Obviously, this is only my opinion and, as such, can be wrong.

  • Paul

    Also the experienced phisicist Zichichi failed, many years ago, in replicating Focardi’s cell on LENR at CERN not founding excess heat, but it was his fault not Focardi’s! I read that paper in comparison with Focardi’s papers, and LOL…

  • Gerard McEk

    It is good that people are critical about the measurements or effects they encounter during experiments. I am sure F&P would know about these effects, as e.g. McCubre is. Small effects during many tests done should take these heat effects into account and include them in their analysis. I welcome this critical note!

    • bachcole

      McKubre

  • georgehants

    PhysOrg
    Hydrogen breakthrough could be a game-changer for the future of car fuels
    http://phys.org/news/2014-06-hydrogen-breakthrough-game-changer-future-car.html

    • Gerard McEk

      I read that also George, but the problem with hydrogen is that you cannot easily make it. The whole cycle is inefficient at this moment. The best way to is to make hydrogen from water, but efficiencies above 50% are only reached in labs. The most popular way (from cost point of view) is to make it from oil or natural gas, but than you throw away a lot of energy. If you add another inefficient ammonia stage, then the whole process cycle becomes even less efficient from energy point of view, so I doubt it will be able to compeet with

  • Donk970

    Again and again it needs to be said that LENR is currently in the Edisonian phase of discovery. At some point, hopefully sooner than later, someone will unveil a working power plant that runs for days, weeks, months or even years on nothing but a small amount of hydrogen or deuterium. At that point, like Edison’s light bulb, we may not fully understand the science but we will know how to build one. Eventually we will understand the science but we don’t have to understand it to exploit the phenomenon.

  • Gordon Docherty

    Put simply, this thesis considers results for mildly exothermic / endothermic reactions involving Palladium nanoparticles.

    Some points that are of interest, however:

    * using different ratios of Protium to Deuterium, the reaction is either mildy exothermic, mildly endothermic, or inert if one of either Protium or Deuterium is (to all intents and purposes) absent.

    * Dissociation of hydrogen by the metal lattice is at the heart of even the explanation of the anomalous heating and isotope effect using the concept of H/D exchange.

    * no mention of lattice saturation (although evacuation and subsequent pressurization of the system up to 1200 torr was performed, although 1200 torr is only around 1.6 bar – by comparison, my car tires are normally between 28 and 36 bar, depending on load)

    * as she states, H/D exchange chemical reaction can explain the results of heat generation and absorption in heterogeneous catalysts at 40 ̊C. However, at temperatures above 200 ̊C I observed heating and cooling that could not be explained by conventional chemistry. As far as I am aware, all current LENR processes require heating to above 186 ̊C to initiate the LENR reaction that produces copious quantities of excess heat.

    * no cohering phononic waves applied, that is no resonance

    * outside of Chapter I and Appendix A, which consider Moddel’s research into ZPEnergy, no mention is made of Casimir cavities or utilization of them in the experiments conducted.

    * the paragraph:

    “The origin of a possible heat generation mechanism in Ni-H systems is unknown and worth looking into. The effort should be applied into careful calibration of the gas-loading system to avoid measurement artifacts, since excess energy generation events from Ni-H systems were reported at the elevated temperatures. To investigate the reaction products different characterization techniques could be used in the same manner described in Chapter VI. The fact that the presence of the nano-features is essential to a successful demonstration of heat production in the material makes one expect that the catalytic properties of Ni metal play a role in initiation of a reaction.”

    on page 89 is interesting. The thesis looked at Palladium nanostructures and the [possible] origin of excess heat generation during loading Pd-impregnated alumina powder with deuterium and hydrogen. It’s focus, in other words, was very specific, measuring one particular configuration subjected to different charging regimes.

    In this respect, the paper was useful and, to rephrase what Alain Coetmeur has said elsewhere on this page:

    “Her results can be divided into 3 parts (viewed from 3 perspectives):

    First, she found that the mild heat generated by some experiments with powders can be explained by Hydrogen/Deuterium exchange. She demonstrated this by baking the Palladium, this drove off water trapped in the experiment, so eliminating the possibility of Hydrogen/Deuterium exchange and hence (demonstrably) addressing the problem: exposing the electrode to open air in the lab, however, let water=hydrogen back into the system, so it is essential in Palladium electrode experiments to keep the electrode away from any air/water.

    Second, for higher temperature experiments of gas loading in powders, she found that hotspots in the reactor fooled even the best calorimeters. Such hotspots occur much more readily in gas-loaded experiments, where heat transfer is poor, than in fluid-based experiments, although should always be considered when performing sensitive measurements (obviously, if the internal temperature raises from 200C to 1200C, these hotspots become less qualitatively significant, although they should still be taken into account).

    Third, she tried to apply her findings to the experiment protocol of John Dash. She finally sees that it cannot explain the result, with the D/H exchange heat accounting for only a part of the power measured overall.

    Finally, in her thesis, she reflects that better, more reliable (defensible) measurements would be obtained using classic (flow) calorimetry rather than thermometry.”

    * Finally, perhaps the title:

    MECHANISM OF HEAT GENERATION FROM LOADING GASEOUS HYDROGEN ISOTOPES INTO PALLADIUM NANOPARTICLES

    would have been better re-written as:

    CONSIDERATION OF EXPERIMENTAL ERROR AND ONE POSSIBLE MECHANISM OF HEAT GENERATION FROM LOADING GASEOUS HYDROGEN ISOTOPES INTO PALLADIUM NANOPARTICLES

    So, some useful points, but nothing that says “F&P were wrong”, especially, as has been pointed out elsewhere, what they witnessed was the dramatic meltdown of an unattended reactor overnight through a marble lab bench to leave a deep hole in the lab floor. This may be “mildly exothermic” as compared to the detonation of a thermonuclear device, but I, for one, would not like to have had my feet under that reactor as it went into melt-down. Still, safer than when a spark ignites a natural gas leak… A runaway LENR boiler may wreck the room it was in, but a runaway methane / propane gas leak will definitely blow your house sky high – yet gas boilers are, apparently, safe for domestic use…

    • Gerard McEk

      I agree with your analysis Gordon, although I believe that your tires may explode if you would pressurise them to 28 bar, let alone 36 bar.

      • Gordon Docherty

        :) Yep, that would be some mean machine…

        I meant, of course, 2.65 bar to 3.20 bar (28psi – 36 psi). The problem of typing these things during coffee breaks. Still, that’s just my car tires. Apparently, most LENR experiments have been reported as working in the range of 5 -10 bar (3750 – 7500 torr). It would probably have been better to say it that way.

        …. still, maybe there’s some mileage in hyper-inflated tires :o)

  • Gerrit

    I am a bit disappointed by some of the reactions to the thesis here on this forum.

    When I read about this thesis about a year ago, I was happy to see that cold fusion can be a topic for a PhD thesis. In the history of CF this had not happened before. It’s great it that regard.

    Also the study itself is a good job, as Alain notices below.

    As I am convinced there is something (or many things) yet to be uncovered in this area I am not disappointed that in this study the “real thing” couldn’t be reproduced. I am happy that many false postitives were investigated.

    I wish there would be many more PhD theses on this subject.

    • Gordon Docherty

      Totally agree with the sentiment – this thesis should be seen as a call to further action, not a “game over” call to bury LENR. That, I think, is why the reactions are as they are.

  • Sanjeev

    The P in PhD has nothing to do with western thinkers. Philosophy is just love of knowledge – philos and sophos (something like that)

  • Gordon Docherty

    In Italy, as elsewhere, people are often awarded a degree in philosophy for engineering. Wikipedia (well, it’s sometimes useful) has more info on this:

    http://en.wikipedia.org/wiki/Bachelor_of_Philosophy

  • Sanjeev

    Proceedings of the 14th Meeting of Japan CF Research Society, JCF14

    December 7 – 8, 2013 Tokyo Institute of Technology, Japan

    jcfrs.org/file/jcf14-proceedings.pdf

    They did get CF working with Pd-D/H wet system. I wonder why the mentioned student failed, she should have learned it from the real masters.

    • Sanjeev

      Probably her thesis guide is someone from MIT ;-)

      • US_Citizen71

        As posted last fall Dr. Dmitriyeva was part of the Quatum Engineering Laboratory at CU Boulder. I do not think her thesis was intended to be a hit piece. Several more papers with her as a co-author can be found at the link below.

        http://ecee.colorado.edu/~moddel/QEL/LENR.html

        • Sanjeev

          I’m aware of her contribution and presentations in ICCF etc. I was only joking (and so I put a wink there).

          • US_Citizen71

            No worries, I just didn’t want the mob to get unruly for no good reason! : )

  • Barry8

    Fleischmann wondered if the palladium he purchased for the experiment was for some reason optimal for CF experiments, where someone conducting across the country with palladium purchased somewhere else may not be as optimal. I believe this is very viable. He went back to the original source and they said they only had a foot and a half left.

  • Zeddicus Zul Zorander

    Hmm, I thought McKubre is convinced that the palladium – hydrogen reaction works and even had it replicated several times. At this point I’m more convinced that an engineer such as McKubre who has measured excess heat repeatedly which can only be explained by nuclear reaction is correct than theory number X dismissing this.

    And of course there are hundreds of other studies on archivx confirming nuclear reactions in PD-H2 systems. Not sure what this study is supposed to tell us.

  • georgehants

    The way I see it, if you want the rainbow, you gotta put up with the rain.
    Dolly Parton

    • Zeddicus Zul Zorander

      That’s deep and funny at the same time :)

      Still enjoying your comments, George. Keep it up!

      • georgehants

        ZZZ, and I enjoy yours and many others working for the betterment of this World.
        Us really old people, like Peter and GreenWin are nearly past all the hard work to be done. Ha
        Looking to the youngsters to join the crusade for Truth.

  • georgehants

    From Cold Fusion Now
    “Science Inspired by Martin Fleischmann”
    A new book Developments in Electrochemistry: Science Inspired by Martin Fleischmann has been published by John Wiley.
    From the description:
    Martin Fleischmann was truly one of the ‘fathers’ of modern
    electrochemistry having made major contributions to diverse topics
    within electrochemical science and technology. These include the theory
    and practice of voltammetry and in situ spectroscopic techniques,
    instrumentation, electrochemical phase formation, corrosion,
    electrochemical engineering, electrosynthesis and cold fusion.
    http://coldfusionnow.org/science-inspired-by-martin-fleischmann/

    • http://www.lenrnews.eu/lenr-summary-for-policy-makers/ AlainCo

      the fact that in that “companion book” you find 18 chapters on mainstream calorimetry and 1 on cold fusion, in the middle, show that this book respect F&P/LENR work.

      that this books is published now is an event.
      as if the electrochemist community was preparing to rehabilitate F&P, who were honored before the cold fusion tragedy.

      this is huge, some under-scientist raising their middle finger to APS, after decades of submission.

    • Sanjeev

      This looks like an important book and likely deserves a blog post.
      Strangely the publication date is Aug 2014 here:
      http://as.wiley.com/WileyCDA/WileyTitle/productCd-1118694430.html

  • Andreas Moraitis

    I just found the following paper by Dmitriyeva & Moddel on „Test of zero-point energy emission from gases flowing through Casimir cavities“:

    http://www.sciencedirect.com/science/article/pii/S1875389212024959

    Some time ago we had a discussion about a possible role of the Casimir effect in the context of Rossi’s E-Cat. This study is not about hydrogen, but some noble gases and nitrogen, which makes it even more interesting.

  • Broncobet

    She must have found something pretty interesting or why, as AlainCo said, is she working in the same field in the same city,on the very subject? And felt it too important to share? And she convinced some one with a lot of money to support the enterprise.

  • Broncobet

    This is very interesting, I went to the coolsience site they are doing work with Pa and Pd an angel investor so no need for the government. It would be wild if you visited them on a cold Boulder night and the gas and electric meters weren’t tuning but it was toasty warm.So now I know what ICCF-10 means.

  • bachcole

    Just one more body throwing itself under the wheels of the Juggernaut.

  • Job001

    Logical, zero positive CF results are totally due to chemical effects.
    Wrong materials and conditions, logically gives no CF results.
    Yep, I looked all over the bedroom for my socks that I left in the den, logically I didn’t find them.
    I’m a good looker but a poor finder, that’s logical.
    Logically, negative results prove nothing, as always.
    Likewise, the big results 14+COP have been proven that these are NOT due to chemical artifacts.

  • MasterBlaster7

    I would like to get Mitchell Swartz’s take on this thesis.

  • http://www.lenrnews.eu/lenr-summary-for-policy-makers/ AlainCo

    About critical work, it is quite classic in science, and cold fusion among it. Charles Beaudette in the preface of Excess heat tell how he decided to follow that topic :

    “It was on a lark that I attended the fifth international conference on cold fusion in April 1995. As a retired electrical engineer, MIT 1952, I was looking for something new to hold my interest. At the conference, I saw that those in attendance were competent scientists doing serious research. I reached that conclusion simply by noting the quality of their technical presentations, by participating in discussions with them, and by watching them extend sharply pointed criticisms to one another’s work. At the very least, the best half of them were so. Many had been honored by their associated institutions. Professional meetings often have their Saturday morning sessions for topics irreverently referred to as nuts and fruits. The cold fusion conferences were no exception to this rule.

    Where much of the investigation involved the technical literature, I was pleasantly surprised to find that its best technical papers were up to the standard that I was accustomed to from my days in engineering. The talk of lax peer-review proved to be rumor-mongering. I could find no commentary or analysis of such a lack in the literature. That condition allowed at least a preliminary conclusion that they would provide useful insights into the field.”

  • http://www.lenrnews.eu/lenr-summary-for-policy-makers/ AlainCo

    The title is wrong, bu the study is a good job.

    I’ve read it after a remark on the italian skeptic blog fusionnefredda.

    you should check with real scientists (too bad Edmund storms is no more on vortex).

    Her job is 3 part.
    first she found that the mild heat generated by some experiments with powders was due to Hydrogen/Deuterium echange. She then show that baking the palladium solve the problem, but that letting the electrode in open air in the lab, let water=hydrogen get into again.

    Second for higher temperature experiments of gas loading in powdersn she found that hotspot on the reactor, despite a good instrument, was fooling the calorimeter.
    This problems may happen in gas loading experiment where the heat transfer is not as good as in fluid.

    Third she tries to apply those findings to an experiment protocol by John dash.
    Shhe finally see that it cannot explain the result, and that the D/H exchange heat account for few of the measured power.

    She finally say that better measurement should be done by classic (flow) calorimetry and not by thermometry.

    what we see is classical skeptic scientic work, trying to identify artifact and solve false positive.

    by comparison it shows not only her ethic, different from the wikipravda myth, but it show that some practice of Fleischamnn&Pons (baking, string natural stirring of the water, measurement of recombination) were very good decision, fruit of experience. It also support the work of McKubre, done in pressurized cells, with long experiments, and flow calorimetry.

    this paper is more an evidence of the slef criticism of LENr community.

    She presented papers at ICCF18 (on thermal modeling) and work for Coolescence, a LENr company.

    all but a denial paper, but just a “be careful of false positive” paper. good science!

    see how MFMp suffered and how Edmund Storms bashed them at the beginning. calorimetry is tricky and the physicist who faile to do it properly at the beginning, concluded that it was calorimetry the problem, not their competence.

    • fritz194

      Good Job, indeed.
      But having done some serious project with Geiger tubes recently – especially with almost the same tube used – I found at least some tiny bug/typo on p.31.
      She introduces the used Geiger tube as “LND tube model 07-27″.
      But there is no LND model 07-27.
      “07-27″ is the datecode of that tube.
      You can verify that at p.32 a) – here you can see the datecode “07-27″.
      If you compare it with b) you see something “-16″ – so probably the tube broke or whatever and the new one had a different datecode.
      From the size/shape its the “famous” “LND 712″ or similar with mica window at the end.
      http://www.lndinc.com/products/711/
      As you can see in the datasheet – there is no valid range given for ambient pressure during storage and operation.
      But because its a tube – it definitely has one.
      At least she considers leakage at p.33 as possible reason.
      Contacting the mfgr. would be better – and is almost free of charge.
      But that´s just a minor detail…

  • jousterusa

    I sure was happy to see these words: “for which H/D exchange reaction does not provide an explanation…” I think this is hionest work, although there is, I think, a possibility that the reaction she describes does not mean a nuclear reaction must be discarded as an explanation. I get the feeling she feels that they are not mutually exclusive. BTW, I think it’s “artifact,” not “artefact.”

    • http://www.lenrnews.eu/lenr-summary-for-policy-makers/ AlainCo

      she raise some artifact in her powder experiments, at low temp with D/H exchange, at high temp with hot spot.

      does not apply to wet cells like F&P (negligible), to tight cells, to flow calorimetry…

    • ecatworld

      Thanks Joe — I must have been thinking about one of our faithful posters here!

  • Buck

    Strange.

    If I recall correctly, ‘mildly exothermic’ reactions absolutely do not equate to what triggered F&P’s intense curiosity: the dramatic meltdown of their unattended reactor overnight through the lab bench and deep into the floor.

    Please correct me if my recollection is wrong.

    • http://www.lenrnews.eu/lenr-summary-for-policy-makers/ AlainCo

      right, she talk of HER experiments (negative, false mildly positive).
      Good to warn enthusiastic colleagues (MFMp style) of the tricks of calorimetry on mild reactions.

    • Maxfield Q Norse

      If no one else believes in you, the janitor does.
      Someone should find the janitor, what an interesting interview after all these years.

      • Buck

        LOL . . . your perspective reminds me of a quote about the hubris of intellect: “The Mind will always be a child”

  • Pekka Janhunen

    I remember seeing this at some point. She found some chemical reactions that might occur in FP cells and which were mildly exothermic, but of course without having access to actual anomalous heat producing experiments she couldn’t draw (or shouldn’t have drawn) any firm conclusions. I have seen Olga Dmietriyeva’s name in some CF meetings, after her thesis work, and if I recall correctly, her later work is not as negative to CF as the thesis.

    • http://www.lenrnews.eu/lenr-summary-for-policy-makers/ AlainCo

      she works for coolescence… so if it was so negative and she was convinced all was an artefact, she would do something else

    • Warthog

      The D2/H2 exchange as a source of heat is actually fairly well known, and has been reported several times in various ICCF talks. The amount of heat, however, is insufficient to account for many of the truly intense CF incidents that have occurred (Pons/Fleischmann’s reactor meltdown, Arata’s “boiloff” excursions, and some others.

      The skeptics re-discover it every few years, because they don’t bother to actually read the CF research papers at Jed Rothwell’s LENR/CANR.org site.

      • http://www.lenrnews.eu/lenr-summary-for-policy-makers/ AlainCo

        “The skeptics re-discover it every few years, because they don’t bother to actually read the CF research papers at Jed Rothwell’s LENR/CANR.org site.”

        very good answer !
        I remind the reaction of Ed Storms on MFMP rookies. (and i’m not even rookie)

        • Warthog

          I suspect that even if the author “had” read the LENR/CANR reports, she was probably told “not from a peer-reviewed source……..you can’t use it as a reference.”