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Title of article CLUSTERS OF WATER IN THE COMPOSITION OF ANTIFREEZES
Authors

Miroshnikov A.M. , Kemerovo Institute of Food Science and Technology (University) , alexandr_mirosh@mail.ru

Esina Z.N. , Kemerovo State University , st. Krasnaya 6, Kemerovo, 650043 Russia

Gushhin A.A. , Kemerovo Institute of Food Science and Technology (University) , bul'v. Stroiteley 47, Kemerovo, 650056 Russia

Ushakova N.N. , Kemerovo Institute of Food Science and Technology (University) , bul'v. Stroiteley 47, Kemerovo, 650056 Russia

Section: CHEMISTRY AND ECOLOGY
Year 2015 Issue 1 DOI 10.12737/11468
Annotation Antifreezes based on water eutectics are widely spread in engineering and by crio-preservation of biological objects as well. Salts of inorganic and organic acids, alcohols, glycols, glycol ethers, glycerin, acids, bases, amino-acids, and other chemical compounds are suitable here as supplementary means. Part of these compounds is capable to take part in the formation of H-bonds with water molecules, the others do not form H-bonds (CaCl2), but they are united into crystal-hydrates of CaCl2•6 H2O type. In this case H-bond of water molecules can become the bond of intermolecular-cluster type. It is assumed that basic structural components of liquid water are cyclic penta- (H2O)5 and hexamers (H2O6), built with the participation of the long hydrogen bond and capable of producing the crown effect. Cyclic water clusters - short-range order of water in terms of cavity size and the number of oxygen atoms correspond to crown ethers: 15-crown-5 and 18-crown-6, sodium and calcium ions being absorbed into them. Energy estimation of water and ice (snow) interaction with the components of antifreezes: ethylene- and diethylene glycols, ethylene glycol ethers, hydrogen chloride and ammonia is made. Possibility of “ideal” solution formation with low freezing temperatures is shown. The analysis of the eutectics and diagrams of water antifreeze fusion based on the salts, alcohols, ethylene glycol, ethylene glycol ethers, hydrogen chloride and ammonia by comparison with an ideal solution of water concerning cryoscopic constant is carried out. It is established that the coefficient K in the equation of linear melting curve y = K·x + b for effective antifreezes, in terms of freezing temperature, exceeds the cryoscopic constant of water, that testifies to the destruction of long-range order of water. Penta- and hexamers of water responsible for short-range order of water pass into the eutectics as monomers or oligomers with the degree of cross linking equal to 2-4. To create effective antifreeze it is important to avoid the destruction of cyclic water clusters. It is desirable, as in the case with ethylene, to have the second component of water antifreeze in a cyclic form too. There is an analogy with naphthenic (cyclic) hydrocarbons of oil, which provide mobility of the condensed state. Promising are antifreezes based on mixtures of inorganic and organic compounds.
Keywords Water clusters, penta- and hexamers, H-bond, antifreeze, water cryoscopic constant, crown-effect
Artice information Received March 26, 2015
Accepted April 8, 2015
Available online June 30, 2015
Imprint article Miroshnikov A.M., Esina Z.N., Gushhin A.A., and Ushakova N.N. Clusters of water in the composition of antifreezes. Food and Raw Materials, 2015, vol. 3, no. 1, pp. 126-131
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Bibliography
  1. Krasnova, K.S., Fizicheskaja himija (Physical Chemistry), Moscow: Vysshaja shkola Publ., 2001, 512 p.
  2. Unger ,F.G., Fundamental'nye i prikladnye rezul'taty issledovanij neftjanyh dispersnyh sistem (Basic and applied research results of oil disperse systems), Ufa: GUP INHP RB Publ., 2011, 262 p.
  3. Kirsh, Ju.Je., and Kalnin'sh, K.K., Osobennosti associacij molekul vody v vodno-solevyh i vodno-organicheskih rastvorah (Features of associations of water molecules in water-salt and aqueous-organic solutions), Russian journal of applied chemistry, 1999, vol. 72, iss. 8, pp. 1233-1246.
  4. Grishaev, A.A., http://www.o8ode.ru/article/learn/newstructure.htm.
  5. Mishhenko, K.P., and Ravdelja, A.A., Kratkij spravochnik fiziko-himicheskih velichin(Quick Reference physico-chemical variables), Leningrad: Himija Publ., 1972.
  6. Kratkaja himicheskaja jenciklopedija v 5 tomah (Brief Chemical Encyclopedia in 5 volumes), Moscow, Sovetskaja jenciklopedija, 1961 - 1967.
  7. Jennan, A.A., and Lapshin, V.A., O svjazi temperatur zamerzanija so stroeniem vodnyh rastvorov (On the relationship between freezing temperatures and the structure of aqueous solutions), Russian Journal of Physical Chemistry, 1975, no. 9, pp. 2295- 2301.
  8. Poling, L., and Poling, P., Himija (Chemistry), Moscow: Mir Publ., 1978.
  9. Zimakova, P.V., and Dymenta, O.N., Okis' jetilena (Ethylene oxide), Moscow: Himija Publ., 1967.
  10. Shahparonov, M.I., Mehanizmy bystryh processov v zhidkostjah (Mechanisms of fast processes in liquids), Moscow: Vysshaja shkola Publ., 1980.
  11. Esina, Z.N., Miroshnikov, A.M., and Korchuganova, M.R., Enthalpy of phase transition and prediction of phase equilibria in systems of glycols and glycol ethers. Foods and Raw Materials, 2014, vol. 2, iss. 1, pp. 86-90.
  12. Miroshnikov, A.M., Guschin, A.A., Ivanov, G.V., and Ushakova, N.N., Vodnye klastery v sostave antifrizov [Water clusters in the composition of antifreezes]. Tehnika i tehnologija pishhevyh proizvodstv (Food Processing: Techniques and Technology), 2014, no. 3, pp. 114-120.
  13. Chudnov, A.F., Nauchnye osnovy kompleksnoj pererabotki olefinov v oksidy olefinov i ih proizvodnye. Avtoref. diss. dokt. tekhn. nauk (Scientific bases of complex processing of olefins into olefin oxides and their derivatives. Dr. tech. sci. autoabs. diss., Tomsk, 1997.
  14. Miroshnikov, A.M., and Ushakova, N.N., Tehnologija pishhevoj dobavki E 1520 – propilenglikol' (Technology of food additive E 1520 – propyleneglycol) Teoreticheskie osnovy pishhevyh tehnologij (Theoretical bases of Food Technology), Moscow, Koloss Publ., 2009, pp. 1341 - 1351.
  15. Voronkov, M.G., and Knutov, V.I., Makrogeterocikly (Macroheterocycles), Moscow, Znanie Publ., 1988.

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