Camosciata

Department of Chemistry of the University “Federico II” of Naples, Via Mezzocannone 4,
80134 Naples , Italy - E-mail Elia@chemna.dichi.unina.it

An extensive thermodynamic study has been carried out on aqueous solutions obtained through successive dilutions and succussions of 1% in weight of some solutes up to extremely diluted solutions, (less than 1x10-5 mol kg-1) obtained via several 1/100 successive dilution processes. The interaction of acids or bases with the extremely diluted solutions has been studied calorimetrically at 25°C.
Measurements have been performed of the heats of mixing of acid or basic solutions, having different concentrations, with bidistilled water or with the extremely diluted solutions. Despite the extreme dilution of the solutions, an exothermic heat of mixing in excess has been found, in about the 92% of the cases, with respect to the corresponding heat of mixing with the untreated solvent. Here we show that successive dilutions and succussions may alter permanently the physical-chemical properties of the solvent water. The nature of the phenomena here described still remains unexplained, but significant experimental results are obtained.

A thermodynamic study on aqueous solutions gives interesting information about the behaviour of solutes and their interactions with the solvent. The interaction of acids or bases with the extremely diluted solutions have been studied calorimetrically at 25°C.The extremely diluted solution is obtained starting from a solution at 1% in weight. After succussion, that solution is named 1CH preceded by the name or formula of the solute.
The succussion process consists in vertical shakings of the solution by means of a mechanical apparatus. In a simple succussion process, one hundred vertical strokes in six seconds are given to the glass vessel containing the solution. To prepare the successive dilution 1 g of this solution is added to 99 g of water that again gets succussed, obtaining the 2CH solution. The iteration of this process gives the extremely diluted solutions studied. Measurements have been performed of the heats of mixing of acid or basic solutions, having different concentrations, with bidistilled water or with the extremely diluted solutions.
Procedures for the calorimetric determination of the heat of dilution or mixing are well developed (Ref.1). The experimental results are treated according to the MacMillan-Mayer (Ref.2) approach, modified by Friedman and Krishnan (Ref.3). The enthalpies of mixing two solutions are given by the following equations:

DHmix(J kg-1) = hxx mfx(mfx- mix) + 2hxymfxmfy+ hyy mfy(mfy- miy) + higher terms

where mfx, mfy, mix, miy are the molalities (mol kg-1) after and before the mixing process, respectively, and hxx, hyy and hxy the enthalpy interaction coefficients, are adjustable parameters. Their values fall in the range 1x102-1x104 J kg mol-2. Consequently, when the concentration of the solute y of an extremely diluted solution is of the order of 10-5 mol kg-1 or less, while the concentration of the solute x is a finite one:1x10-4-1x10-2 mol kg-1 the previous equation reduces to the sole contribution of x. This actually happens on the third successive 1/100 dilution. Then, the extremely diluted solutions, as those described before, because of the practical absence of the solute, cannot produce any contribution to the heat of mixing via the y component. For electrolyte solutions, the powers of the molalities in the previous equation are fractionary, but the conclusions stay absolutely the same.
By an extensive study it was assessed that, using aqueous solutions of acids or bases as reagent, it is possible to distinguish qualitatively the behaviour of pure solvent from that of the extremely diluted solutions, whose chemical composition is the same as that of the solvent used. The interaction between acids or bases with the extremely diluted solutions has been studied calorimetrically, determining the heats of mixing at 25° C by means of a Thermal Activity Monitor (TAM) from Thermometric (Sweden).

The heats of mixing with the solvent (bidistilled water) and those with the extremely diluted solutions, were determined. Sodium hydroxide (NaOH) or hydrochloric acid (HCl) aqueous solutions, at a concentration of 0.01 mol kg-1, were used as reagent, while the concentrations of the extremely diluted solutions were less than 1x10-5 mol kg-1. Despite the extreme dilution of the solutions used, an excess exothermic heat of mixing has been found in about the totality of the cases, with respect to the heat of mixing of the same reagents with the solvent.
The excess heat of mixing, namely the difference between the heat of mixing of the reagent (a solution at finite concentration ) with the extremely diluted solutions and the heat of mixing of the same reagent with the solvent, is of the same order of magnitude or higher than the heat of mixing of the reagent with the solvent. To explain this heat in excess we are forced to focus our attention on the solvent and, in particular, on possible chemical-physical changes induced by the procedure employed in preparing the solutions.

The excess heats of mixing of about three hundred experimental measurements, using as reagent aqueous solutions of NaOH or HCl 0.01 mol kg-1, are reported in columns 1-5 of Table 1, together with the heats of mixing of the same reagent with the solvent. The reported heats in excess are detectable for some weeks.
From this Table it clearly appears that a new phenomenon occurs and, because of the absence of solute, it can be inferred that the physical-chemical properties of the solvent must be permanently altered by the procedure of successive dilutions (1/100) and succussions, used to prepare the extremely diluted solutions.
Thus, we can firmly state that it is now easly possible to measure a chemical-physical property, the heat of mixing with acids or bases, characterizing this new state of the water (Ref.4-6), using a commercial microcalorimeter.

To confirm these very surprising findings, but otherwise “objective” instrumental responses, and to get a deeper insight into this new behaviour, a calorimetric titration procedure was adopted. The excess heats of mixing, thus produced in about three hundred experimental measurement, are reported in columns 6-13 of Table 1.
A “titration” of the extremely diluted solutions implies the determination of the heat of mixing in excess, with respect to the heat obtained with the reference bidistilled water, when solutions of NaOH at different concentrations are mixed with the samples under examination. About 60 titrations have been performed with about 40 different samples. These titration curves present two peculiar features (see Fig. 1). First, a plateau appears at the highest concentrations of the titrant, and, second, there’s a “break” point at a concentration of about 0.001 mol kg-1 of the reagent used (NaOH) in the final solution. This latter feature and particulary the fact that it appears exactly at the same concentration, is commom to all experiments (with different samples of the extremely diluted solutions used). On the other hand, the magnitude of the excess heat, characterizing the plateau, depends on the nature of the solutions.

To test the stability of these chemical-physical changes in water “structure”, the extremely diluted solutions were further diluted (withouth the succussion procedure) in different proportions (e.g. 1 : 1, 1 : 2,..) with bidistilled water. These “simply diluted” solutions were “titrated” with the NaOH solutions . The resulting curves are characterized by plateaux which are proportional to the degree of the “simple” dilution (i.e. for the proportions just cited as examples, 1/2, 1/3 of the plateaux obtained with the original samples of the extremely diluted solutions), but showing the “break” points at the same concentration of the reagent used (Fig. 1). This means that the modifications in water “structure” induced by the preparation procedure are stable with respect to a normal dilution process and that the reagent interacts via a destroying mechanism, revealing a pH-dependent phenomenon.
Fig.1 reports titration curves for a highly diluted sample. For the sake of comparison,
Fig. 2 shows typical calorimetric titration curves for an acid-base reaction, obtained titrating two solutions of the acid, whose concentrations are in the 1: 2 ratio. As it can be seen, two different plateaux are reached and two different equivalent points are identified, both in the 1 : 2 ratio, thus showing a sharp difference, either in the amount of heat, slope of the curves and equivalent point positions, with respect to the behaviour of the extremely diluted solutions for which each “titration” curve reaches its own plateau, at the same “break” point.
It is very interesting to look at the heat of mixing vs pH diagrams (see Fig. 3 ): they reveal an extraordinary similarity with the normally reported ones for a two-state, pH induced denaturation process of proteins.( Ref.7)

The exact nature of the phenomena here described still remains unexplained, but significant experimental results have been obtained. The mixing process of acids or bases reveals a statistically significant exothermic excess heat with respect to the same process carried on the untreated solvent, bidistilled water, despite the physical absence of solute molecules in the solution obtained after just a few dilution/succussion procedures.
All that is not, at present, in agreement with current theories concerning the properties of liquid water at room temperature (Ref.8) and consequently, the need for new appropriate theoretical studies urges.

A hypothesis of disorder-order transition could be proposed, based on the exothermic excess heat and its pH dependence, induced by the addition of acid and/or basic reagents.

References

1.Castronuovo, G., V. Elia, & F. Velleca. 1997. Hydrophilic interactions determine cooperativity of hydrophobic interactions and molecular recognition in aqueous solutions of non electrolytes. The preferential configuration model. Current Topics in Solution Chemistry, 2,125-142.

2. MacMillan, W.G. & J.E. Mayer. 1945. The statistical thermodynamics of multicomponent systems, J.Chem: Physs., 13, 276-305.

3. Friedman, H.L. & C.V. Krishnann. 1973. Studies of hydrophobic bonding in aqueous alcohols: enthalpy measurements and model calculations. J. Solution Chem., 2, 119-140.

4. Davenas, E., et al. 1988. Human basophil degranulation triggered by very dilute antiserum against IgE, Nature, 333, 816-818.

5. Lo, S.Y. 1996. Anomalous State of Ice, Modern Physics Letters B, 10, 909-919.

6. Lo, S.Y. et al. 1996. Physical Properties of Water with IE Structures, Modern Phys. Letters B, 10, 921-930.

7. Privalov, P.L.1973. Stability of proteins. Small globular proteins, Adv. Protein Chem , 33, 167-241.

8. Franks, F., 1976. Water. A Comprehensive Treatise Plenum, New York.

Table 1. Excess heats of the mixing for extremely diluted solutions with sodium hydroxide and hydrochloric acid solutions.

System	-Q g NaOH 5x10-3 me	N d	-Q g HCl 5x10-3 me	N d	-Q g NaOH 2.5x10-3 me	N d	-Q g NaOH 1x10-3 me	N d	-Q g NaOH 5x10-4 me	N d	-Q g NaOH 2x10-4 me	N d
H2O bidista	2.1±0.1a	30	0.85±0.01a	30	1.7±0.1a	30	1.4±0.1a	30	1.0±0.1a	30	0.5±0.2a	30
H2O 1 CH b,c	0f-10	21	0.4-0.6	12	0 f -9.8	11	0 f -7.9	11	0 f -3.3	11	0 f -2.1	11
H2O 3 CH b,c	0 f -38	52	0 f -3.2	35	0 f -35	18	0 f -11	18	0 f -5.9	18	0 f -3.6	18
H2O 30 Hb,c	0.8-16	35	0 f -5.8	26	1.5-3.4	4	1.4-3.1	4	1.1-2.9	4	0.5-1.7	4
NaCl 3 CHc	0 f-17	31	0 f -3.3	19	1.3	1	1.3	1	1.2	1	0.8	1
NaCl 30 CH c	0 f -16	25	0 f -1.5	19	-	-	-	-	-	-	-	-
IAA 7 CH c	2.4-3.8	2	-	-	2-3.6	2	2-3.1	2	1.8-2.7	2	1-1.6	2
IAA 8 CH c	3.1-4.5	2	-	-	3-4	2	2.7-3.7	2	2.4-3.1	2	1.4-1.6	2
IAA 9 CH c	1.4-3.1	2	-	-	1.4-3	2	1.3-2.6	2	1-2.2	2	0.4-1.2	2
IAA 10 CH c	8.3-9.3	2	-	-	8-9	2	7.1-7.9	2	5.7-6.2	2	2.7-2.9	2
IAA 11 CH c	4.5-7.9	2	-	-	4.3-7.6	2	3.8-6.6	2	3.2-5.5	2	1.6-2.9	2
IAA 12 CH c	0 f -4.9	12	-	-	3.8-4.8	12	3.3-4.1	12	2.9-3.4	12	1.7-1.8	12
2,4-D 3 CH c	2.6	1	-	-	2.5	1	2.1	1	1.7	1	1	1
2,4-D 5 CH c	0 f	1	-	-	0 f	1	0 f	1	0 f	1	0 f	1
2,4-D 7 CH c	1.6	1	-	-	1.2	1	1.2	1	0.8	1	0.3	1
2,4-D 8 CH c	1.6	1	-	-	1.5	1	1.2	1	0.9	1	0.6	1
2,4-D 12CH c	0.5-2.6	6	-	-	0.2-2.4	6	0.2-2.4	6	0.2-1.8	6	0.2-1.1	6
GLP 4 CH c	0 f	1	-	-	0 f	1	0 f	1	0 f	1	0 f	1
GLP 5 CH c	0.6	1	-	-	0.6	1	0.4	1	0.3	1	0.1	1
GLP 6 CH c	0.3	1	-	-	0.3	1	0.2	1	0.1	1	0.1	1
GLP 7 CH c	0 f	1	-	-	0 f	1	0 f	1	0 f	1	0 f	1
GLP 8 CH c	0.4	1	-	-	0.4	1	0.4	1	0.3	1	0.1	1
GLP 9 CH c	1.1	1	-	-	1	1	1	1	0.8	1	0.4	1
GLP 10 CH c	4.9	1	-	-	4.6	1	4.2	1	3.4	1	1.8	1
GLP 11 CH c	3.5	1	-	-	3.3	1	3.1	1	2.5	1	1.2	1
GLP 12 CH c	0 f	1	-	-	0 f	1	0 f	1	0 f	1	0 f	1

Sodium chloride: NaCl, Indole-3-acetic acid: IAA, 2,4 dichloro phenoxyacetic acid: 2,4-D, N-(phosphonomethyl)-glycine: GLP. a Heats of dilution (mean ± SD) of sodium hydroxide solutions. b In these cases the procedure of preparation starts with pure solvent. Succussion and dilution is performed just as in the cases of 1% solutions.c Because of the quantitative variability of the excess heats of mixing for these systems, the range of values obtained is reported.d Number of experiments performed. e Concentration (mol kg -1) of the reagent after the mixing process. In these experiments the final concentration is half of the initial one.
f Percentage of experiments that give null excess: 8%. g Excess heats of mixing (J / kg ) of the extremely diluted solution.

Table 2. Excess heats of mixing in the titration of the extremely diluted solutions with sodium hydroxide.

mNaOH a	-Q b IAAc 12 CH	-Q b IAAc 12 CH diluted 1:1	-Q b IAAc 12 CH diluted 1:2
2.10-4	1.1	0.5	0.2
5.10-4	2.7	1.3	0.55
1.10-3	3.5	1.6	0.6
2.5.10-3	4.1	2.0	0.85
5.10-3	4.1	1.9	0.85

a Concentration (mol kg -1) of the reagent after the mixing process. In these experiments the final concentration is half of the initial one. b Excess heats of mixing (J / kg ) of the extremely diluted solution. c Indole-3-acetic acid: IAA

Table 3. Excess heats of mixing in the titration of hydrochloric acid with sodium hydroxide.

mNaOH a	-Q b HCl 1. 10 -3 mol kg -1	-Q b HCl 2. 10 -3 mol kg -1
2.10-4	19.7	19.7
5.10-4	57	57
1.10-3	57	116.2
2.5.10-3	57	116.2
5.10-3	57	116.2

Legends

Figure 1. Calorimetric titration curves: Extremely diluted solutions of IAA 12CH ( ) and its 1 : 1 ( ) and 1 : 2 ( ) normally diluted solutions with bidistilled water.

Figure 2. An example of calorimetric titration of at 2x10-3 ( ) mol kg -1 HCl solution and its 1 : 1( ) diluted solution with bidistilled water.

Figure 3.Calorimetric titrations curves: Extremely diluted solutions of IAA 12CH ( ) and its 1 : 1 ( ) and 1 : 2 ( ) normally diluted solutions with bidistilled water, as a function of the pH in the final solutions.

Origine, diffusione e caratteristiche economiche

Razza con standard originaria del Veneto. E' stata selezionata dal prof. A. Ghigi presso la Stazione sperimentale di pollicoltura di Rovigo, partendo da un gruppo di faraone bianche acquistate nel 1922 all'esposizione internazionale avicola di Parigi. Differisce dalla faraona bianca per la pelle del corpo pigmentata: quella della gola e del collo appare nerastra. Non molto allevata. Le uova di faraona presentano un guscio molto duro e si prestano sia per il consumo fresco che per la preparazione di paste alimentari. La femmina depone circa 100-120 uova per ciclo (peso medio 45 grammi, guscio di colore rossastro). La durata dell'incubazione è di 26-28 giorni.
La maturità sessuale viene raggiunta a otto-nove mesi nei maschi e a circa sette-otto mesi nelle femmine.

Caratteristiche morfologiche

Livrea bianco giallastra con chiare perlature evidenti; tarsi da grigio chiaro ad arancio pallido. La pelle del corpo è pigmentata mentre quella del collo e della gola è nerastra.
E' oggi tra le faraone quella con mole più ridotta.
Peso medio:
- maschi adulti 1,8 kg
- femmine adulte 1,8-2 kg

Faraona di razza Camosciata - Adulto e faraoncini a poche ore di vita

Caratteristiche esteriori per il riconoscimento del sesso

Elmo: nella femmina è più smussato mentre nel maschio è più largo alla base e più curvato all'ndietro.
Bargigli: nel maschio sono maggiormente sviluppati, presentano una superficie ondulata e picchiettata e sono maggiormente rivolti in avanti rispetto a quelli della femmina. Nel maschio si potrebbero definire accorciati in avanti, nella femmina piatti ed aderenti alla faccia.
Faccia: la pelle della faccia nel maschio rispetto a quella della femmina è più allungata e scende maggiormente ai lati del collo chiudendosi in forma appuntita.
Portamento: nella femmina è quasi orizzontale, mentre nel maschio è più eretto.
Peso: le femmine sono un po' più pesanti dei maschi.

Camosciata Atlante delle razze di Faraone

Origine, diffusione e caratteristiche economiche

Caratteristiche morfologiche

Caratteristiche esteriori per il riconoscimento del sesso

Camosciata
Atlante delle razze di Faraone