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The EEC phenomenon (cf. e.g. Lui & Guo ref. 1), a possible
manifestation of the Le Chatelier principle, the basis of
which only became apparent following the development of
Fluctuation Theorem concepts, creates stochastic
outcomes of chemical reactions (e.g. seen as random
ligand exchanges and randomization of structural breakup
and reformation (ref. 2)), is the basis of the Hammett and
Taft empirical linear free energy relationships (LFERs) (cf.
Leffler ref. 1) as well as the Meyer Neldel Rule in
semiconductor physics (Liu & Guo ref. 1 and ref. 3) but
perhaps the most commonly reported type of EEC is
revealed by a comparison of sets of chemical reaction rate
constants (the Arrhenius rate constants
kr = Ae-Ea/RT (eqn. 1) for thermally induced chemical
reactions (refs. 1)) which counter-intuitively, more often
than not are found to obey a common inter-relationship
=logA/ Ea (eqn. 2, cf. Leffler ref. 1) ) { logA
E
(eqn. 2a)}.
Under EEC-compliant situations the enthalpic (Ea) and
entropic A terms in eqn. 1 become phenomenologically
linked by some unknown mechanism; (i.e. they are not
independent variables as is required by classical
thermodynamics). This linkage allows a single EEC effect
to influence the detailed outcomes of different classical
rate-determining chemical reaction mechanisms. An
example of this effect is seen with the thermal
dehydrochlorination of all substances having a common
structural feature, (the presence of H-C-C-Cl bonds) which
loose HCl upon heating by a single EEC-compliant process.
Here a single EEC (eqn. 2) applies to a surprisingly wide
range of different reaction conditions e.g. where the
dehydrochlorination occurs in the gas phase by an initial
rate determining homogeneous scission, or in the gas
phase heterogeneously with the involvement of free
radical chain reactions, or with the presence of absence of
SEEC
aSEEC
The coupling of heat and entropy changes arising from space fluctuation is of
relevance to a fuller understanding of the relative stability of chemical molecules.
Such fluctuation is also indicated to be the ultimate origin of EEC via how a
complex time fluctuation of the vacuum space between the subatomic particles in
chemical molecules determines the observed rate of transition state complex decay.
Let the energy of fluctuation be Ef = h and the entropy of fluctuation S f = /
[n (ln + / - be (the sum of such entropy in the number (n) of space compartments/unit volume)
where is an EEC-compliant time meter (e.g. a direct time reversal with + and - as in this expression or an
equivalent imaginary time fluctuation time meter).
Since the frequency of fluctuation creates both the energy and entropy effects
which can be considered separate space and time fluctuation processes;
but general relativity connects space and time; this creates the apparent nonthermodynamic link-up of supposedly independent enthalpic and entropic terms
which appears as the EEC phenomenon.
which means that EaSEEC cannot, as previously believed, arise from an activation process using energy
derived from a conventional kinetic energy transfer process, i.e. from the real particle kinetic energy
system. The very general nature of the SEEC phenomenon per se requires that we consider an
additional source of SEEC activation energy. Such a source is the virtual kinetic energy processes
involving the type of supposed virtual particles or vortices which are thought to define the energy
system of the vacuum.
FIG.1 (vide infra) shows a 60 data set of kr=Ae-Ea/RT where again the logA (x) and
Ea (y) values seem to be related directly viz. logA
Ea ; the trend-line again
goes through the 0,0 origin with the standard least squares fit scatter factor R2 of
0.9473).
This dataset contained 45 data points from 1968 plus 14 additional dehydrochlorination data points reported by
Zho & Bozzelli in 2002;
(the 1968 set had been retrieved by data mining from the abstracted peer-reviewed dehydrochlorination reaction Arrhenius rate
equation literature database in an industrial lab. in the context of using a computer modelling system of gas phase reactions
which required that all reported such rate constants be assembled. The listed data unexpectedly showed up correlations between
the numbers in the lists of rate factors. This indicted that the current theories of space time must be incorrect. However the
current theories well so well entrenched that other than private discussion of the aforementioned possibility seemed not to be
easily achievable.
The R2 scatter between the pre-1968 and post 2000 data point is similar. This indicates that the putative underlying vacuum
energy driving force is similar between these data sets.
FIG. 1
Other EEC sets similar to FIG. 1 (but with only a few data points were reported
Leffler ref.1a, cf. also vide infra).
Ea log A
FIG. 2
FIG. 2 shows data from dehydrochlorination rate constants determined during experiments
specifically carried out to model polyvinylchloride decomposition (reported by Z Mayer in
Thermal Decomposition of Poly(vinyl Chloride) and of Its Low-Molecular-Weight Model
Compounds 1974 Marcel Dekker, p. 282 et seq.
FIG. 3
117 dehydrochlorination rate constant which includes data (from A Maccoll et al. loc.
cit.) which had been used to argue against the existence of EEC per se.
References
(1) Key EEC-related refs are:
Lui and Q.-X. Guo Chem Rev 2001 101 673-695,
J.E. Leffler J Org Chem 1955 20 1202-1231
D Chodera and DL Mobley Annu Rev Biophys 2013 42 121-41
had been by
FH Constable Proc Roy Soc London 1925 108A 355-375, cf. ref. 1 in Liu & Guo
(2001) loc. cit.
Cf. also the early report of EEC by DHR Barton AJ Head and RJ Williams J Chem. Soc 1951 20392046
EEC effects were also reported but not discussed by
Z Mayer Thermal Decomposition of Polyvinyl Chloride) and of Its Low Molecular Weight
Model Compounds
Marcel Dekker Int. 1974 p. 282-9
L Zhu JW Bozzelli Chem Phys Lett 2002 366 445-52
Other papers relating to dehydrochlorination reaction kinetics given to me in 1968 by an ICI colleague (PJ Thomas) who had
been a co-worker of A Maccoll at U. Col. London, included info rel. to DHR Barton and coworkers cf. DA Blackadder and
Cyril Hinshelwood J Chem Soc 1958 2728 (General discussion of energy-entropy relations
who had thought that the existence within a compensated set of rate constants of very high (irrational) values of log A might
be explained by an exotic process in which a combinations of distant bond vibration energies could somehow be channelled
into a specific reacting chemical bond was suggested by (but this apparently was considered later not to be a credible
hypothesis).
Cf. also M Ullah et al. Appl Phys Lett 2010 96 213303 and D Grant scribd 2012 A Hypothesis 1a37
(web)
Examples of other reports of EEC
H. Campbell and D.D. Eley Trans Faraday Soc 1940 36 854-856.
I.M. Barclay and JAV Butler ibid., 1938 34 1445-54.
[the Barclay-Butler effect (a sub-set of the EEC effect) provides a probe for the structure of liquid water in mixtures
cf. AR Henn and W Kauzman Biophys Chem. 2003 100 (103) 205-220],
J.K. Middleton et al. J Virol 2002 76 1051-1061,
O.K. Vorov et al. Biophys J 2009 97 (11) 3000-3009
[Thermal deactivation of Reoviral infective subparticles is mediated by the denaturation
of a viral surface protein {n.b. reoviruses are nonenveloped viruses}]
Several papers report compensation during food processing e.g.
C.I. Beristain et al. J Food Engineering 1996 30 405-415
[Water vapour adsorption on food]
P.C. Moyanici et al ibid., 2004
[Browning]
and, for hydrogen adsorption on zeolites etc. (cf. web)
Cf., for the related electronic physics
EEC effect (the Meyer Neldel Rule) see, e.g.
EEC in Geology
Cf. A Yelon et al. Rep Prog Phys 2006 69 1145; cf. ref (4)
EEC in Cosmology
The enthalpy-entropy compensation effect may contribute to cosmic scale correlations (where log entropy is
plotted vs. log mass) cf. Menas Kafatros e-book web Problem of Observation and Cosmology and the Big Bang .
D Grant 2012 web Scribd 96573303 A Hypothesis1a37 (the first half of this document
presents a preliminary general discussion of the general-throughout-science EEC effect).
The Fluctuation Theorem (cf. ref. 5) and the various EEC phenomena which shows up in various forms throughout chemistry,
biology, physics, (and possibly also in geology and cosmology, cf. ref. 1) apparently arise because of a deeper requirement for a
stochastic deterministic balance. This means a consideration of the association between EEC, Fluctuation Theorem determined
stochastic behaviour in chemistry can offer insight into the general-throughout-science stochastic deterministic balance law. This
especially concerns a new formulation of time along the lines suggested by the Fluctuation Theorem which gave critical insight
into the scope of the second law of thermodynamics, and more generally allows a major reappraisal of the status of determinism
in nature.
Examples where the second law is replaced by the Fluctuation Theorem (i.e. where stochastic rather the deterministic functions
are required to be used for internal energy) are found e.g. in fluid mechanics (cf. ref. 5b) where the spontaneous increase in
entropy required by the second law is replaced by a significant amount of decrease in entropy are found in Couette flow where he
second law violation can occur for several seconds (not therefore as sometimes stated Fluctuation Theorem reverse entropy
does not only arise for very short periods of time). This applies to cholesteric liquids (cf. AR Henn W Kauzman New
considerations of the Barclay-Butler rule and the behaviour of water dissolved in organic solvents Biophys. Chem. 2003 10
205-220 (n.b. the Barclay-Butler rule is a sub-class of EEC).
Similarly the formation of micelles is a Fluctuation Theorem related process as is the formation of vortices which jump about
(fluctuate) in fluids (e.g. in industrial mixers).
The perturbation of an underlying linear dependence of entropy and enthalpy change can also be used systematically to probe the
structure of aqueous solutions containing water and in Brownian motion a similar process seems to cause the observe
Fluctuation-Theorem-determined motion of a bead towed through water (see ref. 5).
It also seems likely that the R Feynman anything goes as regards the electron in time and space is an example of the dominance
of stochastic behaviour of the makeup of the quantum vacuum and idea which can be extended to suggest that all chemical and
physical interactions. However a complex rather than a real number time process may apply to the gives rise to the
EEC effect producing Fluctuation (with a probability which depends exponentially on entropy x time).
(5) Cf. G.M. Wang et al. Phys Rev Let 2002 89 05061
This paper produced experimental evidence of Fluctuation Theorem entropic variation in liquid water and
offered the first experimental proof of a reversal of second law entropy generation for less than one micro sized
particles suspended in water over two seconds time.
(5a) Cf. The recent illustration of how Fluctuation Theorem related stochastic effects determine fluid
mechanics and related processes is set out in the paper by M Ostofa-Staraewski entitled Second law
violations, continuum mechanics and permeability Continuum Mech. Thermodynamics DOI
10.1007/s00161-015-0451-4. (Here it is shown that entropy can be considered to be a submartingal).
The spacetime fluctuation process must also therefore apply to all chemical molecular time variations and hence the EEC effect
and how time fluctuation is related to this by a relativistic fluctuation of space-time resonance can be suggested to arise by the
frequency of this resonance being the principal driver of the rate of chemical reactions.
Fluctuation can alternatively be predicted to arise from vacuum fluctuations according to traduitionaly quantum mechanical
theory; cf.
which
describes theoretical calculations using QED theory which seem to indicate that molecular complexity information might be
exported from the vacuum into liquid water.
Cf. also Water 2010 2 566-586.
The reality of the existence of the (potentially complex structured) electromagnetic quantum vacuum is also demonstrated by the
Casimir effect, the Lamb shift, spontaneous emission, van der Walls bonds and the Ahranov Bohm effect.
The Casimir cavity effect in water capillaries may enable the formation of water superstructure (perhaps mimic that of the
vacuum subspace e.g. having a grain structure of sizes around 1nm) and be the energy source of the Pollack water layers at
sulphonated surfaces and also of the Wiggins high and low density forms of water (information about these concepts are avail. by
using them as web search terms).
[Cf. P. Ball July 2013 Edition of Chem. World (Royal Society of Chemistry, London) alluded to the
del Giudice hypothesis of water superstructure generation via a quantized vacuum field effect in the
context of how ghost DNA homeopathy might arise].
(5d) JA Macken in a treatise entitled The Universe is only Spacetime (web) takes forward previous
ideas about why the energy of the vacuum could be the driver of all observed phenomena. Macken
especially succeeds in explaining why the totality of this energy (which eludes observation by
cosmological methods) dominates the quantum mechanical interpretations of the universe which now
includes gravitational waves afforded by Planck scale spacetime vacuum energy vortices (rotars).
The fundamental particles and forces of physics arise out of a single-vacuum field system. This
hypothesis does not discuss the Fluctuation Theorem and its associated EEC phenomenon which
disallows the deterministic view of the universe replacing it with a stochastic universe (which rqruies
the occurrence of a dramatic reversal of time in parts of space) and therefore Macken does require to
consider the evdidence the reversal of time is a valid concept; he instead restricts his discussion to rate
of relativistic time diminution (i.e. a small scale process, i.e. time reversal occurs but only slightly) for
space restriction as required by general and special relativity.