, Dr Relton was working as a homeopath who had contact with some of the 103 participants given either a homeopathic remedy known as carcinosin or a dummy drug. Although the study found no statistically significant clinical improvements among those taking homeopathic treatments compared with those on a placebo
https://www.sciencedirect.com/science/article/abs/pii/S0022399903003775?via%3Dihub
Portions of the structure have to be cut, which induces spurious electronic density variations at the border of the cluster. To remove these dangling bonds, the border of the cluster is usually saturated by H atoms. These atoms are however at the origin of deviations of electronic properties from that of the full solid
Why we saturate the terminal bonds in [[cluster model]]s
For catalytic materials and reactions, most of the time, such an approach is however not sufficient, because we are dealing with variable coordination for surface species, due to dangling bonds at the surface and the existence of defects, and due to the catalytic reaction itself. In such cases, quantum chemistry needs to be considered.
drawbacks of #[[molecular mechanics]]
mpact on the zeoliteís properties (structure, acidity) is poorly understood
effect of binders
there is still a debate on the nature of the Br ̄nsted acid sites on ASA
Goodkind et al.[11]concludedthat in 2018“each $1 of Bitcoin value created was responsible for $0.49in health and climate damages in the US and $0.37 in China”
toll et al.[2] estimated that the carbon footprintproduced by Bitcoin mining“sits between the levels produced by thenations of Jordan and Sri Lanka”
natural framework silicoalumin-ates where, however, cations (usually alkali or alkali earth) are located in relativelylarge cavities in the interior of the [Si1−xAlxO2]x−negatively charged framework.These cavities are connected by channels that give rise to a variety of microporousstructures, which can be penetrated only by sufficiently small molecules, so givingrise to the “molecular sieving” effect [177] as well as the “shape selectivity” effectin catalysis [178,179].
They conclude that the resultsobtained with pyridine, as a probe is an artifact. In our opinion, this however, isonly the result of the much stronger (more than harder) basic character of pyridinewith respect to CO, which allows it to compete (unlike CO) as a base with sulfateions, which are also bases
CO vs pyridine do study Lewis acid sites
“reactive” amines inprinciple are as nonspecific as ammonia in adsorption
Gorte's reactive amines
give an integral response ofthe phenomena occurring upon interactions, without giving information on theirquality
Calorimetric techniques
After all this, it seems at this point that still there are no truly useful probes for distinguishing materials with respect to acid strength, and one should rely on reactivity.
the co-adsorption of the strongly basic trime-thylamine and NH3 has provided, for the first time, an infrared evidence of four distinct acidic hydroxyls in defect-free HY. These sites have different acidic strengths and provide therefore various coordination environments to the ammonia and ammonium species inside the sample
[[Probe molecules]] [[co-adsorption]]
Mrs. Fonda carried a small whip in her right hand, and she cued the horse by waving it. I detected Mrs. Fonda doing it every time the horse moved the lettered blocks with the nose. This method of doing the trick might have puzzled me if I hadn't known that the placement of horse's eyes on either side of the head gave them wide backward range of peripheral vision. Therefore it offered no problem for me to detect. Mrs. Fonda, when cueing Lady Wonder, stood about two-and-a-half feet behind, and approximately at a 60-degree angle to Lady's head. The shaking of the whip first time was the signal for Lady to bend her head within a couple of inches to the blocks. A second shake of the whip was the cue for Lady to continuously move her head in a bent position back and forth over the blocks. When Lady Wonder's head was just above the desired block Mrs. Fonda made the horse touch the block with her nose by shaking the whip a third time. It was as simple as that.
[[John Scarne]]
found the owner would intentionally signal the horse with a whip as LadyWonder moved her head over the blocks, preparatory to nudging them intowords
[[John Scarne]]
strong possibility that Mr. Fonda at times played the role of a confederate, for Rhine tells us in his first article that Mr. Fonda was present "part of the time," but since he played a very inconspicuous role in the proceedings, "we leave him out of the account for thesake of brevity." In brief, Rhine's "controls" were laughably inadequate
Mr. Fonda could acted as guide however it was ignored from [[J B Rhine]]'s work
n the late 1970’s, one is still distressed to read assertions, by a self-proclaimed “cen- taur,” that horses communicate by means “more subtle than man himself extrasensory perception and telepathy.
Great ability of horse for ESP
dubbed the mare Lady Wonder “the greatest thing since radio,”
[[J B Rhine]] about [[Lady Wonder]]
we were forced to conclude that the telepathic abilitywe earlier found the horse to possess has been now almost ifnot entirely lost and that Lady has become merely a trained animalconditioned to a system of signals made up of indicative bodymovements, voice inflections, whip movement
Lady lost its telepathic ability
It was clear, therefore, that the animal was accus-tomed to taking its cues from the individual who stood at its head{F's accustomed place) rather than from the one who stood infront and across the table from it
When they move further from the horse's head they were not able to give cues to the horse and the tests failed. Having Mrs. Fonda away from Lady with Rhine in the middle showed that Rhine could easily override the influence provided by Mrs. Fonda
R himself, standing at the horse's headwas able to direct it by voice inflection and body movements soi;hat it touched the desired blocks or cards with very few fail-Tires
Rhine was able to guide the horse when he tried
under the conditionsused in obtaining the earlier successes, Lady was no longer sus-ceptible to influence from R as agent. His attempts to direct theanimal mentally were failures not only when he stood in front ofit with eyes shaded from it and from F, but even when he stoodat its head with eyes unshaded
Rhine as the guide fails
There is left then, only the telepathic explanation, the trans-ference of mental influence by an unknown process. Nothing wasdiscovered that failed to accord with it, and no other hypothesisproposed seems tenable in view of the results
Conclusion
TABLE I
Results show a clear influence of Mrs. Fonda
F with closed eyes. R watched her. M mixed blocks, F and Rnot seeing them thereafter. Thus F and R alone knew theletter chosen and no one knew its location.Tests 1-2. Letters T, F.Result: 1 incorrect after three trials, 1 incorrect after two trials.The horse's movements lacked their usual definiteness. Shetouched or nodded sometimes at a block (wrong), sometimesbetween two of them, in an apparently random fashion.This series shows that knowledge of the location of the chosennumber by someone present is necessary, and that the knowl-edge of which letter it is is not enough. In series IX c and dit was shown that knowledge of the location alone was sufficient.These tests suggest, therefore, that the horse does not know theletters and that superior intelligence is not a factor
Important test and conclusion
Numbers: 6, 8, 4, 0, 3.Result: 4 correct, 1 correct on second trial
With Rhine
Numbers- 3, 8, 9, 5, 8, 8, 2, 4, 3, 5.Result: 9 correct, 1 correct on second trial
With McDougall
Numbers chosen. 2, 7, 4, 0, 2, 9, 6, 8, 3, 1.Results: 9 correct, 1 correct on second trial. (F spoke duringtests 1 and 2.)
Mrs. Fonda knew the numbers, she was silent but allowed to move freely
Tests 1-10. Numbers: 4, 6, 4, 0,1, 7, 3,1, 9, 4.Result: 5 correct, 3 correct on second trial, 2 incorrect
Mrs. Fonda was not allowed to look to Lady but held the whip. Rhine reports that Fonda look several times at Lady. There is a decrease in the number of correct answers
Where does Mr. Thomas go from here? (He went to Detroiteventually, which F knew, but first to New York City, whichF did not know.) Detroit—C
Evidence of Mrs. Fonda cue
Tests 1-5. Words: bed, kid, Mesopotamia, Carolina, Hindustan.Results: All correct
Spelled all the words correctly without knowing the words, however, Mrs. Fonda knew the words and this were the unrestricted tests
8 correct, 1 incorrect (no second trial given except wherespecified), and 1 untried. The cube root of 64 was the incorrectone, and that of 1,728 was not tried
Results for arithmetic calculations
F talked freely to the horse and used the whip occasion-ally when necessary to urge her to work. F sometimes caughtLady's halter and drew her back for a fresh start. In movementssuch as these, and in the words and inflections of her spoken com-mands, we naturally looked for evidence of a system of guidance
Unrestricted testing
Most of the observersagreed, with the committee, that unconscious signals from theinvestigator guided the horse. Some suspected that a stable man,whom they supposed was hidden about the place, gave the signals.Pfungst (6) claimed to be able to guide the horse by signals him-self.
[[Clever Hans]]
conducted 500 tests on the mare. In the end, he could find no hoax and declared that the horse had considerable psychic abilities. In later years, he observed that perhaps Fonda had been subtly signaling Lady Wonder, though he would not elaborate.
J B Rhine
Stone said sometimes hundreds appeared in a single week, many of them seeking help from the horse in playing illegal numbers games
Ivey Stone neighbor of the Fondas
Debye–Hückel theory
can be used to calculated activity coefficients. It can be done easily and gives accurate results for low and medium concentrations
The deviation of the real(red curve) from the ideal (blue curve) behavior depends onthe ability of the solvent molecules to shield electrical chargesfrom each other, which means that it depends on the dielectricconstanterof the solvent. The highereris, the higher is therange of concentrations over which ideal behavior prevails.The deviation of real from ideal behavior is expressed by theactivity coefficientf
which is unity for ideally dilute solutions
real proton gas would explode in a huge Coulombexplosion with an energy equivalent to millions of atomicbombs
pure sulfuric acid hasa pH value of 1.55. However, according to Equation (1), a 1maqueous solution of HCl has a pH value of around zero
If only [[Søeresen equation]] we could be tented to conclude that a 1M solution of HCl is more acidic than pure HCl. This indicates that the pH value, as defined by the [[Søeresen equation]] is not suited to compared acids in different media
it does not describe the potential of the protons toprotonate a reaction partner in a medium
[[pKa]] describes the degree of dissociation of an acid compound in a medium
Acidity, quantified by the pH value, is theability or (more precisely the potential) of protons in a mediumto protonate a reaction partner in this medium
activity can be traced back to the chemicalpotentialmof the solute
Look for activity in http://goldbook.iupac.org/
Sørensen equation
pH = -log a(H+)
where a(H+) is the activity of the proton
The questionnowarises,whethersuchwatermoleculescanbe foundexperimentally,oranothercharge-balancemodelexists
e propose that the triad nests in SSZ-70 are bestdescribed by a cyclic model, although the DFT calculationsoverestimate the strengths of the hydrogen bonds
The authors considered a cyclic and a non-cyclic models which the DFT calculation gave (6.35, 7.17 and 7.68 ppm) and (3.10, 7.46 and 8.60 ppm) while the experimental is (3.1, 4.2 and 5.5 ppm), respectively. The authors selected the cyclic model because "their span agrees much better with the experimental values"
Jones and Iglesia calculated IR band frequencies for allpossible BAS configurations in zeolite ZSM-5 and significantred-shifts were found for certain positions which these authorscorrelate with a confinement parameter for the Brønsted acidicproton
The new1H NMR signals that onlyexist in MFI-60 and not in MFI-14 or MFI-20 clearly must beassigned to hydrogen-bonded SiOH groups as bridging OHgroups, Si−O(H)-Al, can be ruled out, since these signals arealso found for Na-MFI-60
It may also arise from protons that were not exchanged by Na in inaccessible site, where the Brønsted acid site can in fact make more hydrogen bonds with the framework.
isopropylamine
Is there any [[1H NMR]] or [[15N NMR]] studies of [[isopropylamine]]-loaded zeolites? #[[to review]]
efect silanol groups at 1.8 and 2.1 ppm are moreabundant inFigure 1D than inFigure 1A. Obviously, thesesilanol groups are subject to some defect healing under thethermal conditions of the conversion treatment of Na-MFI-60to yield H-MFI-60
The conversion of [[NaZSM-5]] to [[NH4ZSM-5]] resulted in the decrease of [[1H NMR]] resonances assigned to both [[internal]] and [[external]] [[SiOH]] species.
3.0 BAS per unit cel
This values is too high since the #[[Si/Al ratio]] = 60 has only 1.6 Brønsted acid sites per unit cell
ines at 6 ppm for H-MFI-14and H-MFI-20 was previously interpreted as being due tohydrogen-bonded BAS
It as only been assigned to remains of [[water]] #[[1H NMR]]
Figure 1
The 1H signals at 1.8 and 2.1 ppm are assigned to external and internal silanol defect sites without hydrogen bonding
The extent of dissociation of protons in condensed liquidacids, the property measured by acidity functions,47however,would be enhanced by the solvating environments around themolecular groups. Thus, acid strengthandsolvationeffectsareconflated in empirical acidity scales and the two must be sepa-ratedtodeciphereffectsofthereactivesiteandtheenvironmenton reactivity and selectivity trends for broad classes of acids
DPE values do not depend on the species that wouldultimately accept the proton, whether such species are titrants,bound intermediates, or transition states;
acid strength and the size andshape of the voids combine to determine reactivity, but theinteractions that these two properties of solid acids mediatediffer in origin and magnitude. Electrostatic and covalenteffects are responsible for the consequences of acid strengthon catalysis while weak concerted van der Waals forces, result-ing from induced dipoles, account for the effects of confine-ment
new applications of solid acids in the processing of biomass, a solvent will be present. Understanding the effects of different solvents will be critical for achieving a fundamental understanding of these reactions and more work is needed in this area
xtra lattice aluminol species in zeolites created in the presence of water, with rates reportedly influenced by the proximity of these aluminols to framework Al atoms
does not show reaction in 2-propanamine TPD and is not able to protonate pyridine in the absence of water [44]; however, since the material shows activity for H-D exchange with toluene-h8 [29], it must be considered a Brønsted acid
in-situ titrations of acidic zeolites at elevated temperatures [36,37]
heats of adsorption for NH3 at Brønsted sites are not a useful predictor of catalytic activity. It has been shown that ∆Hads for NH3 on Brønsted sites formed by framework Fe in ZSM-5 were identica
proton transfer from the acid site to the base is incomplete but hydrogen-bond strengths still correlate with PAB