Solvation excesses in the water solutions of D-glucose, saturated by humic acid
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1 Solvation ecee in the ater olution of D-glucoe, aturated by humic acid A. Pendin 1, S. Karabaev, I. Gainullina, A. Kharcheno, S. Lugovoy 3, N. Gridaova 1 St.Peterburg tate univerity, Ruia, pendina@mail.ru Kyrgyz- Ruian Slavonic univerity, Kyrgyztan, arabaev_@mail.ru 3 Ariel Univerity Center of Samaria, 47 Ariel, Irael Abtract Effect of preferential olvation in the ater olution of D-glucoe, aturated by humic acid (HA ere decribed in the term of ece value. Autoecee in binary olvent and olvation ecee of D-glucoe over the ater on humic acid ere calculated by ue of coefficient activity data in to- and threecomponent ytem. Analytical character of dependence of autoeee from mole part of monoaccharide ater olution component a determined in the frame of ideal aociated olution theory. Analyi of olvation ecee of D-glucoe over the ater on humic acid a given in coordinate of Hill, graph. Etimation of humic acid molecular enemble ize in ater olution of monoaccharide a held by ue of olvation and urface Gibb, ecee. Key ord Humic acid, D-glucoe, olvation ece, autoece, Gibb urface ece, olubility, coefficient of activity. Introduction In or [1-] a hon that for olution of non electrolyte for hich permiible chemical reaction are reaction of homo and hetero aociation, upport equation (1 can be ground. d ln y i( j d ln a (1, i T, P, al K here i ( j - olvation ece (SE of i particle over j particle in olvation urrounding of particle; y -rational coefficient of activity of particle; ai -activity of i particle; T - temperature; P - preure; l i, l j. In equation (1 phyical meaning of olvation ece (SE of i particle over j particle in urrounding of mole particle i determined by equation (. r C Ni i( j ( i j 4r dr (, V here r C - radiu of molecular correlation, N i -number of i part in volume V, i ( j - radial function of ditribution. 185
2 In equation ( value of olvation ece ( i ( j i mean tatitical quantity of i particle on hich olvation hell of particle i richer in comparion ith j particle, proceed from compoition of binary olvent i-j. If in olvation urrounding of particle relation of i and j particle number are equal of it relation in the volume of olution non indignant by particle, then. In thi cae preferential olvation i abent. i( j Equation (3 are conequence of equation (, here,, - mole part of i, j, component [1,]. i j K i K i( j j( i j K K i K i( j i( l j( l j l K 1 K K i ( j (3 Eitence of binding equation (3 reult in that in binary ytem from for olvation ecee only one independent, in three component ytem from eighteen ecee only for ecee are independent. Range of permiible value of i ( j i determined by condition of tability of concentration change []. Concept of olvation ece a uccefully ued for decription of preferential olvation in uual multicomponent liquid olution [3-5]. Uing of ece thermodynamical value method for biochemical ytem and micelle olution a decribed in fundamental or. Aim of our reearch i uing of olvation ece concept a analog of Gibb adorption in the volume of the phae for decription of effect of preferential olvation in the olution of lo molecular ligand, containing natural biopolymer. It ha practical interet to determine olvation ece of monoaccharide (, a product of metabolim of g living ytem, on humic acid (g in ater olution (. Equation (4-6 can be ritten and ued for calculation of olvation ece in accordance ith equation (1 and (3 for reearch ytem: lgy ( lg a T, P g (4 (5 g (6 lgy lg a T, P, a g In equation (4-6 ymbol ( are autoecee in binary olvent ater-dglucoe, Y g - limiting coefficient of activity of humic acid in ater olution of D-glucoe. Y g 1 at a 1, 1 (mole dole of D-glucoe i equal to. 186
3 Eperiment Humic acid ere etracted from analytical tet of bron coal of Kara-Keche depoit, (Kyrgyztan uing method of Orlov [8]. Reearch imple of humic acid correpond to comple of characteritic ign of molecular enemble ith maimal containing of aromatic carbon (7% and practically full abence of ugar fragment. Izothermal aturation of ater olution of D-glucoe by tudying imple of humic acid from Kara-Keche a carried out at Т=98 К and continuou miing during 4 hour. Phae ere eparated by centrifugation at 4 rotation in minute. Solubility of humic acid ( C at. GK in ater olution of D-glucoe a determined by pectrophotometer at the ave length 4nm. E-value of humic acid in ater olution of monoaccharide i 1 1 Е,3л г см, l 1. Reult of eperimental data of olubility are preented in table. Solubility and limiting coefficient of activity of humic acid in ater olution of D-glucoe ( at T 98 K Table - lg aw C6H1O6 H O( C6H1O6 11 ( 1 C g ( г / л - lgy g g,1,1 -,5-1,4,7,51,19,,6 -,5-1,7,3,149,3,3,11 -,75 -,1,38,1996,46,4,16 -,1 -,4,46,85,59,5,1 -,16 -,8,55,36,7 Logarithm of limiting coefficient of activity of humic acid ( lgy D-glucoe are alo preented in table and calculated by equation (7. нас C ( lg g Ygi lg (7 нас C ( g g in ater olution of Value of ater activity logarithm ( a in ater olution of D-glucoe, Gibb relative urface ecee of monoaccharide over ater (, auto ecee ( in binary olvent ere taen in the or [3]. Reult and dicuion Solvation ecee in the ater olution of D-glucoe From definition of olvation ece (1, binding equation (3 it i clear that for any table tocomponent olution can be ritten inequality (7 1 (7 187
4 At the ame time quetion about limiting value at ( i open and mut be olved on the bae of eperimental data eamination and their etrapolation from the phere of terminal concentration of olvent component on (. A it can be een from table data, autoecee value for ytem ater- ( D-glucoe are negative. Thi reult i conequence of ea hetero aociation of D-glucoe ater olution component. Special interet for control of reerve of olvation ece concept i application of equation (4 for ideal miture of aociated compound. Water olution of D-glucoe correpond to thi condition, becaue ater ( and glucoe ( form vazi ideal olvent at preence of equilibriumw S WS. Notice that thi tatement correpond to idea about mutarotation of D-glucoe in ater olution [9]. In thi cae epreion for rational coefficient of activity of ater and D-glucoe [1] can be ritten a equation (8. y y 1 1 / / (8 Condition of chemical equilibrium of aociate WS formation reaction in differential form d ln d ln d ln allo to calculate private derivative (1, a for ideal miture of compound d ln ai d ln i and a i cont correpond to i cont. Introduce value. n / n n / n n n (9 In equation (9 - i a part of ater (W and D-glucoe (S, connected in aociate (WS, n- mole number. Tae into account that for thee value equation i correctly, here and - mole part of ater and D-glucoe of binary olution 1. Lie that, correlation (1, (8 and (9 allo riting equation (1 for olvation ecee in ater olution of D-glucoe. C 6H1O 6 H O C6H1 6 H O H O( C6H1O6 1 O C H O H O H O H O C H O H O H O C6H1O6 ( H O 1 C6H1O6 C6H1O6 ( H O (1 H O C6H1O 6 C6H1 6 C6H1O6 H O( C6H1O6 1 O C6H1O6 In equation (1 value are olvation ecee of ater over monoaccharide H O( C6H1O6 in monoaccharide olvate urrounding. According to correlation (1 negative defleion C6H1O6 from ideality in ater olution of D-glucoe provide poitive value of, a 188 H O( C6H1O6 binding equation (5 i correctly. In accordance ith equation (1, at formation of C6H1O6 molecular aociate compoition 1:1, bigget value arrive at, H O( C6H1O6 C 6H 1O6
5 moreover they mutn t limit number to. A it can be een from table data value C6H1O6 atify to thee limitation. H O( C6H1O6 Solvation ecee of D-glucoe over ater on humic acid Data of table are the bai of calculation of olvation ecee of D-glucoe over ater on humic acid by equation (6. For thi purpoe dependence lgy f (lg a ere decribed by polynom ith folloing analytical differentiation. Reult of g monoaccharide alvation ecee over ater on humic acid are preented in the table. A it can be een from table, olvation ece of D-glucoe over ater on humic acid g g i poitive and i found in interval. Thi reult tetifie the preferential concentration of urface non-active molecule of D-glucoe on humic acid in ater olution. It i obviou, that olvate activity of monoaccharide i eplained by inter molecular interaction of D-glucoe ith reaction center of molecular enemble of humic acid. For definition of D-glucoe molecule number, imultaneouly binding ith humic g acid, analyi of value of olvation ecee a carried out in coordinate of Scetcherd plot and ithin the frame of Hill emi empirical method [6]. Reult of thi eamination are preented in the Fig.1. g Fig.1. Dependence of olvation ece of D-glucoe over ater on humic acid from compoition of ater olution of monoaccharide in coordinate of Hill plot A it can be een from Fig.1 Hill coefficient ( H i a little maller then unit, it i eplained by ea anti cooperative binding of D-glucoe molecule on four reaction center of tudied imple of humic acid from Kara-Keche coal. So far a contant of humic acid aociation ith four molecule of D-glucoe i not big (К=8,, e can conider that energy of biopolymer interaction ith component of binary olvent i maller than among particle of olvent. In thi cae phenomenological relation beteen g olvent ( and urface ( ecee can be ritten a equation (11 [4]. (11 g P g 4 rg N A 1 ( rg The firt number ( 4 r N g A of equation (7 i the olvation ece of urface-active component of binary olvent on the urface of cavity ( r P, radiu of thi cavity i equal to 189
6 radiu of humic acid in the ater olution of D-glucoe ( r g. The firt correction P g 1 ( rg account the crooedne of thi cavity. The econd correction account the contribution of intermolecular interaction of humic acid ith D-glucoe in g the value of at the bringing of biopolymer in cavity. According to Tolmen [11] for humic acid at r r, ( r. At the ame time, the value of econd correction P g P 1 g can be equal to four molecule of D-glucoe, imultaneouly related ith humic acid g 4. So, equation (11 can be ritten a equation (1. r g ( g 4 N A 4 (1 Reult, carried out by equation (1 are preented in the Fig.. Fig. Dependence of humic acid radiu ( r g from compoition of ater olution of D-glucoe( S A it can be een from Fig. radiu of humic acid lie phere in ater olution of monoaccharide monotonouly decreae from 47 to 31 nanometer ith increaing of D-glucoe mole part in the interval,1, 5. A it can be een from table and Fig. dependence of humic acid radiu from olvation ece i line, limiting value S r g at g ( correpond to r 58 nm. Obviouly, obervation regularitie are S g caued by tructural change of biopolymer eamined imple in reearched compoition of ater olution of monoaccharide. Reference 1. Pendin A.A. Preferential olvation in three- and multycomponent liquid olution // Journal of phyical chemitry P Pendin A.A. Preferential olvation and thermodynamical propertie of nonelectrolyte olution // Journal of phyical chemitry P Pendin A.A., Karabaev S.O., Suareva О.М. Preferential olvation of ferrocen in to component polar olvent // Journal of phyical chemitry Т. LI. N 4. P Pendin A.A., Vailieva L.G., Karabaev S.O., Suareva О.М. Influence of intermolecular interaction of ferrocen in tocomponent olvent on characteritic of preferential olvation // Journal of phyical chemitry V. 64. N 4. P
7 5. Karabaev S.O., Pendin A.A. Effect of preferential olvation of ion and non electrolyte in binary olvent. - KSNU. - B: p 6. Wyman J., Lined function and reciprocal effect in hemoglobin: A econd loo, Adv. Protein., 19, 3 7. Ruanov A.I., Kuni F.M., Shein A.K. Point ecee in theory of uual and micelle olution // Journal of phyical chemitry. 9. V. 83. N. P Karabaev S.O., Lohina I.M., Gainullina I.P., Muabeova Z.R., Kharcheno A.V. Etraction and analyi of humic acid from Kara-Keche coal // Vetni of Kyrgyz-Ruian Slavonic univerity.- 1. V.1, 1.- P Karabaev S.O., Gainullina I.P., Buhueva A.V., Lohina I.M., Subanulova D.A. Influence of the ame type term ion ( 1 S on mutarotation of D-glucoe in ater olution // Vetni of Kyrgyz Ruian Slavonic univerity V P Prigojin I., Defey R. Chemical thermodynamic. N.: Naua, p 11. Adamon A. Phyical chemitry of urface. M.: Mir, p. 191
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