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The retention equation in reversed-phase ion-pair chromatography

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Abstract

In this paper, by combination of the statistical thermodynamic method with the Freundlich isotherm, the retention equations to describe the effects of the mobile phase composition, concentration of the ion-pair reagent and the ionic strength on the amount of adsorbed ion-pair reagent and the retention value of the ionic solute have been reported by simultaneously considering the electrostatic and molecular interaction between solutes, ion-pair reagent and molecule or ion in each phase in the reversed-phase ion-pair chromatography. The validity of these retention equations has been confirmed by calculation of capacity factor of the different phenylamine and naphthylamine sulphonic acids during systematic change of concentration of the strong solvent, the ion-pair reagent and the ionic strength in the mobile phase.

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Abbreviations

a, b, c, d, d 1,e, f, h, g anda′, b′, c′, d′, e′, f∼', g′, h′ :

parameters related to chromatographic system

A :

solute

B :

constant

B i :

solventi

C b andC p :

concentration of strong solvent and ion-pair reagent

C a P :

amount of adsorbed ion-pair reagent

D :

dielectric constant

E AP ,\(E_{AB_i } ,E_{PB_i }\) andE pp :

molecular interaction of adjacent pair of solute-ion-pair reagent, solute-solventB i , ion-pair reagent-solventB i and ion-pair reagent-ion-pair reagent

E a p andE a e :

non-electrostatic and electrostatic adsorption energy of ion-pair reagent

F :

Faraday constant

h :

Planck constant

I :

ionic strength

j A ,\(j_{B_i }\) andj p :

internal partition function of solute, solventB i and ion-pair reagent

k :

Boltzmann constant

k′ :

capacity factor

k p ,n p andk 1,n 1 :

parameters of Freundlich isotherm of ion-pair reagent and solventB 1

K AP ,\(K_{AB_i }\) and\(K_{PB_i }\) :

constants related with the molecular size of solute, ion-pair reagent and solventB i

m A ,m P and\(m_{B_i }\) :

molecular weight of solute, ion-pair reagent and solventB i

N A ,N P and\(N_{B_i }\) :

numbers of solute, ion-pair reagent and solventB i in solution

N a A ,N a P and\(N_{_{B_i } }^a\) :

numbers of solute, ion-pair reagent and solventB i adsorbed on the surface

N s :

number of adsorbed sites on the surface

P :

ion-pair reagent

R :

gas constant

T :

absolute temperature

V 0 :

volume of solution

V p and\(V_{B_i }\) :

volume of ion-pair reagent and solventB

X :

potential function

X 1 P andX l P :

potential function of ion-pair reagent on the surface and in the solution

X a A andX l A :

potential function of solute on the surface and in the solution

Z A ,Z P andZ i :

charge numbers of soluteA, ion-pair reagent and inorganic ioni

Z AP and\(Z_{AB_i }\) :

numbers of ion-pair reagentP and solventB i surrounding the soluteA

ɛ 0 :

permittivity in a vacuum

ϕ :

electrostatic potential of the surface

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Authors and Affiliations

  1. Dalian Chromatographic R. & D. Center of China, Dalian Institute of Chemical Physics, Academia Sinica, Liaoning, People's Republic of China

    Peichang Lu, Hanfa Zou & Yukui Zhang

Authors
  1. Peichang Lu
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  2. Hanfa Zou
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  3. Yukui Zhang
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Dedicated to Professor J. F. K. Huber on the occasion of his 65th birthday

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Lu, P., Zou, H. & Zhang, Y. The retention equation in reversed-phase ion-pair chromatography. Mikrochim Acta 102, 35–53 (1990). https://doi.org/10.1007/BF01244287

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  • DOI: https://doi.org/10.1007/BF01244287

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