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Thermodynamic measurement by gas chromatography at finite solute concentration

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Summary

This paper surveys gas chromatographic methods for making thermodynamic measurements at finite solute concentration. The factors which determine the shape of elution and frontal chromatograms are first described. The retention volume equation is obtained for finite concentration taking into account the sorption effect and curvature of the distribution isotherm. A new and reasonably accurate equation (Equation 20) is then derived for calculation of the isotherm from chromatographic measurements. Comparison is made with an older, much used procedure which is shown to give large errors through neglecting the sorption effect. Experimental results with both accurate and inaccurate procedures are surveyed.

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Abbreviations

c:

molar concentration of solute in gas phase

\(\bar c\) :

value of c (constant along column) for a characteristic point on boundary

\(\overline {\bar c} \) :

value of c for plateau

C:

total molar concentration of all species in gas phase

F(c) or F(y):

flow rate of gas phase, measured at column outlet pressure, carrying a zone which has a constant concentration c (corresponding to an average mole fraction jyo), given by Equation (12)

j:

gas compressibility correction factor (Equation (9))

k:

“capacity factor”, ratio of amount of solute in liquid phase to that in gas phase at equilibrium

l :

distance from column inlet

Pi :

column inlet pressure

Po :

column outlet pressure

q:

molar concentration of solute in liquid phase in equilibrium with c in gas phase

\(\bar q\) :

\( = q\left( {\bar c} \right)\)

\(\overline {\bar q} \) :

\( = q(\overline {\bar c} )\)

R:

gas constant

t:

time measured from injection

tM :

retention time of non-sorbed solute

tR :

retention time of solute

T:

column temperature

u:

velocity of gas phase through a zone of concentration c

VL :

volume of liquid phase in column

VM :

gas holdup (measured with a non-sorbed solute)

V 0M :

=jVM

VR :

retention volume of solute zone of constant concentration c

V 0R :

=jVR

y:

mole fraction of solute in gas phase

yo :

value of y when zone of concentration c reaches column outlet

α:

\( = \alpha ' + \bar y_o t_M \)

α′:

area hatched in Figs. 1–3

β:

area shown in Figs. 2 and 3

η:

skew ratio, ratio of slope of front edge to slope of rear edge of elution peak (measured at points of inflexion)

ρ:

ratio of liquid volume to gas space in column

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  1. Chemical Engineering Department, University College of Swansea, University of Wales, Swansea, UK

    J. R. Conder

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Conder, J.R. Thermodynamic measurement by gas chromatography at finite solute concentration. Chromatographia 7, 387–394 (1974). https://doi.org/10.1007/BF02330941

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