The measurement of organic complex formation constants by gas–liquid chromatography

Cadogan, D. F.; Purnell, J. H.

doi:10.1039/j19680002133

Cited by 38 publications

(14 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[13] In the case of formation of equimolar complexes, a plot of specific retention volumes against acceptor concentration in a liquid phase (V g vs. [A]) is linear, its slope being equal to equilibrium constant. If aggregation of acceptor occurs, a V g vs.…”

Section: Resultsmentioning

confidence: 99%

“…According to Ref. [13] , appropriate solvent should be of the hydrocarbon nature, low melting, and non-volatile. Because, no strong solvents of C 60 with such a complex of properties had been known, we synthesized poly(tetramethylbenzene).…”

Section: Resultsmentioning

confidence: 99%

“…[13] The phases were deposited on Inerton AW (0.20 -0.25 mm; Chemapol, Czech Republic) from solutions in benzene by slow evaporation at 808C. The packings ( were placed into columns of stainless steel tube (l, 1000 mm; i.d., 3 mm) followed by conditioning in a helium flow at 1008C during 6 hr.…”

Section: Gas -Liquid Chromatography (Glc)mentioning

confidence: 99%

See 2 more Smart Citations

On the Nature of Interaction Between Fullerene and Aniline

Borovkov

Blokhina

Kutepov

et al. 2004

Fullerenes, Nanotubes and Carbon Nanostructures

View full text Add to dashboard Cite

Interaction between fullerene C 60 and N,N-dialkyl-substituted anilines was studied by gas -liquid chromatography (GLC) and titration calorimetry. The GLC study was performed at 140-2008C in the poly(tetramethylbenzene) solvent with ultra-high solubility of C 60 . No interaction of the C 60 -aniline type was registered under such conditions. Calorimetric titration performed at 258C in a non-aromatic solvent confirmed the lack of complex formation. Minute exoeffect registered is explained 583 by suppressing of the rotation motion of the C 60 molecules accompanied by energy dissipation for the aniline environment.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

On the Nature of Interaction Between Fullerene and Aniline

Borovkov

Blokhina

Kutepov

et al. 2004

Fullerenes, Nanotubes and Carbon Nanostructures

View full text Add to dashboard Cite

show abstract

“…Since -RlnK = AH°/T -AS° ( 5) the thermodynamic parameters AH°and AS0 are readily obtainable from the Kx data in Table III. The derived values of AH°and AS°are listed in along with their standard deviations.…”

Section: Resultsmentioning

confidence: 99%

Thermodynamics of molecular association by gas-liquid chromatography. III. Aromatic compounds with tetrabutyl pyromellitate

Sheridan¹,

Capeless²,

Martire³

1972

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Equilibrium constants, enthalpies, and entropies of complex formation between benzene, toluene, the xylenes, and mesitylene and tetra-zz-butyl pyromellitate have been determined by gas-liquid chromatography in the temperature range 50-80°. Steric effects were found to predominate over electronic factors leading to the trend benzene > toluene > o-xylene > p-xylene > m-xylene > mesitylene for the equilibrium constants.

show abstract

“…Thermodynamic Association Parameters from GLC Net Retention Volume. When a volatile solute (or Lewis base), B, is injected onto a GLC column, a measure of the total interaction between B and the column packing is given by the net retention volume, Ln:15 Kn = 3 (Pp/Pj)2 The first term in brackets is a correction for the compressibility of the carrier gas and the second term in brackets is the flow rate, fully corrected to 0 °C and the vapor pressure of water (which contributes to the measured flow in a soap bubble flowmeter). P0 and P\ are the pressures (atm) of carrier gas at the outlet and inlet of the column.…”

mentioning

confidence: 99%

Comparison of thermodynamic parameters obtained by gas chromatographic and spectrophotometric methods for the interaction of a Lewis acid transition metal complex with a Lewis base

Chamberlain¹,

Drago²

1979

J. Am. Chem. Soc.

View full text Add to dashboard Cite

For the first time a GLC determination of thermodynamic parameters using solutions of one reactant on the column has been coupled with full corrections for adsorption effects to obtain an accurate enthalpy and entropy for an acid-base reaction in the liquid phase. The system studied involved the interaction of the Lewis base triethylamine with the Lewis acid bis(7,7,11 , I l-tetramethylheptadecane-8,lO-dionato)nickel(II) in squalane. The equilibrium constants, enthalpy, and entropy all compare favorably with those obtained in solution using spectrophotometric methods. Previous studies have yielded different values for the equilibrium constants obtained by the GLC method than from other solution techniques (i.e., spectrophotometric and calorimetric procedures). A new modification of the method for elimination of adsorption contributions has been developed which significantly shortens the time required for analysis. The success of this experiment indicates that data from the GLC experiment may be used in a complementary fashion to standard procedures to determine the reactivity of transitionmetal compounds in solution.For some time gas-liquid chromatography (GLC) has been used to obtain thermodynamic data for acid-base reactions.' Two basic methods have evolved: the neat liquid method, which employs one reactant as a neat liquid phase on the G L C column,* and the solution method, which involves a solution phase on the c o l~m n .~ (This should not be confused with the use of "solution dominated" peaks advocated by Martire and Liao' I for correction of adsorption effects.) Three basic techniques have been developed for adsorption effect corrections without which the thermodynamic data obtained by the G L C methods have little quantitativeRecently we showed that enthalpies of hydrogen-bonding interactions obtained by the neat liquid method for long-chain aliphatic donors are in agreement with those obtained by calorimetric or infrared frequency shift technique^.^ The G L C method used involved pure base on the column and corrections for interfacial effects were made using the solution-dominated approach.8 This study demonstrated that the same enthalpies could be obtained by the G L C method as those for a comparable system in solution.It has been shown that both of the basic G L C methods give the same equilibrium constant for certain systems.I0 It has also been established that the various methods for correction of adsorption effects give the same results.'' However, to our knowledge, no one has coupled the use of the solution method with corrections for interfacial effects to obtain enthalpies that are comparable to those obtained from solution calorimetric or spectrophotometric methods.We are primarily interested in utilizing the G L C technique to determine accurate solvation-minimizedl* enthalpies for acid-base interactions in which the acid is a transition-metal complex. For this reason we have prepared the squalane-soluble compound bis(7,7,11,11 -tetramethylheptadecane-8, IO-dionato)nickel(II), Ni(THDD)2.I3 T...

show abstract

The measurement of organic complex formation constants by gas–liquid chromatography

Cited by 38 publications

References 0 publications

On the Nature of Interaction Between Fullerene and Aniline

On the Nature of Interaction Between Fullerene and Aniline

Thermodynamics of molecular association by gas-liquid chromatography. III. Aromatic compounds with tetrabutyl pyromellitate

Comparison of thermodynamic parameters obtained by gas chromatographic and spectrophotometric methods for the interaction of a Lewis acid transition metal complex with a Lewis base

Contact Info

Product

Resources

About