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An experimental method for testing the solvophobic theory by using graphitized carbon black in GC and LC

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Summary

The net solvent effect for several solute-solvent pairs has been calculated by using the solvophobic approach for describing the liquid chromatographic process. For the same solutes and solvents the net solvent effect has been experimentally measured by using graphitized carbon black columns in GC and HPLC. A comparison between the measured and calculated values made in terms of normalized free energy changes, indicates that the solvophobic theory is fairly adequate for predicting the sequence of solvent strength and provides a comprehensive explanation of the various interactions occurring in reversed-phase LC. Aγ critical discussion of the deviations of the theory from the experimental data is also presented.

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Abbreviations

ΔG netsolvent :

Difference of solvent and gas phase free energy change

ΔGvdw-s :

Standard free energy of solute-solvent van der Waals interaction

ΔGel-s :

Standard free energy change of solute-solvent electrostatic interaction

ΔGc :

Standard free energy of cavity formation

ΔG Ct :

Free energy for transferring solute molecule from gas into solvent (free volume reduction or cratic term)

ΔG assocgas :

Standard free energy change for adsorption reaction in gas phase

ΔG assocliquid :

Standard free energy change for association reaction in solvent

Ia, Is :

Ionization potential of solute and solvent respectively

Da, Ds :

Clausius-Mosotti functions: n2−1/n2+2 where n-refraction index

D :

Function of static dielectric contant, Clausius-Mosotti function at high frequency 2(ε−1)/(2ε+1)

Q′, Q″:

Results from integration of interaction over first solvatation layer. They are dimensionless function which can be calculated by knowing acentric factor (ω) and molecular volume (ν) of solute and solvent

μ:

dipole moment of solute

ra :

molecular radius of solute

va, vs :

molar volume of solute and solvent respectively

N:

Avogadro's number

γ:

Surface tension of solute

A, ΔA:

Molecular surface area and its change during the adsorption process respectively

Ke :

Curvature correction fitting parameter for surface tension

R:

Gas contant

P:

Pressure

K:

Equilibrium constant for solute-carbon adsorption process

ε:

Eluotropic strength defined as log (K′s1/K′s2) = A(ε1 - ε2) where ε2 = 0.

K′:

Capacity ratio. The subscripts GC and LC respectively to gas and liquid chromatography

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Authors and Affiliations

  1. Institut sull'Inquinamento Atmosferioco C.N.R., Area della Ricerca di Roma, Via Salaria km. 29,300, C.P. 10, 00016, Monterotondo Stazione (Roma), Italy

    P. Ciccioli, R. Tappa & A. Liberti

Authors
  1. P. Ciccioli
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  2. R. Tappa
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  3. A. Liberti
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Ciccioli, P., Tappa, R. & Liberti, A. An experimental method for testing the solvophobic theory by using graphitized carbon black in GC and LC. Chromatographia 16, 330–335 (1982). https://doi.org/10.1007/BF02258932

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  • DOI: https://doi.org/10.1007/BF02258932

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