Chem. J. Chinese Universities ›› 1995, Vol. 16 ›› Issue (10): 1597.

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Studies on the Interaction Parameters of the Excess Gibbs Free Energy Between Solutes in Quanternary Mixture

BAI Tong-Chun, ZHANG Xin-Kuan, LU Yan, LU Jin-Suo   

  1. Department of Chemistry, Henan Normal University, Xinxiang, 453002
  • Received:1994-10-19 Revised:1995-05-11 Online:1995-10-24 Published:1995-10-24

Abstract: The retention values of eight organic solutes(i)(benzene,tetrachloromethane,chloroform,dichloromethane,ethyl acetate,tetrahydrofuran,acetone and methyl ethyl ketone)in stationary solution of urea(j)+sodium perchlorate (k)+formamide (s) at 298.15 Khave been measured by a gas-liquid chromatographic method(GLC).The McMillan-Mayer's solution theory,in which all the thermodynamic excess properties of multi-component solution can be expressed by a virial expansion,was used to relate the excess Gibbs free energy of the system to a series of pairs,triplet and higher order interaction parameters. An equation for expressing the relationship between the interaction parameters and the specific retention volume(Vg)of GLCwas obtained,that RTln [Vg(s+j)/Vg(s+j+k)]=2vgikmk+3v2gikkmk+6vgijkmjmkwhere Vg(s+j)and Vg(s+j+k)are the specific retention volumes of organic solutes (i) in multi-component stationary solution of s+j and s+j+k respectively.gik is the pair interaction parameters between i and k, gikkand gijkare the triplet interaction parameters of i-k-k and i-j-k.The values of gk,gijkikkj,mkand Vgdata to the equation given above. Some information about the solute(i)-solute(k) interaction in formamide and the effect of urea on gik have been discussed,For all solutes of i,gik>0,that means the interaction of i and k makes a positive contribution to GiEIn the presence of urea,the gikvalues become more positive than those in the absence of urea,which enhance the salting-out effect on the noneiectrolyte solutes.For the values of triplet interaction parameters,gijk<0,and the contribution of gikkto GiEcan be neglected.

Key words: Gibbs free energy interaction parameter, Gas liquid chromatography, Organic solute, Quaternary mixture

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