Thermal Conductivity Behavior.  Importance in Quantitative Gas Chromatography

Rosie, Douglas M.; Grob, Robert L.

doi:10.1021/ac60129a004

Cited by 82 publications

(27 citation statements)

References 15 publications

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“…These are only correction factor coefficients t o allow for the variation in the response o f the thermal detector. To assume that the response of a thermal detector is the Same for all of the compounds used, is an evaluation which could be capable of over 35% error (40).…”

Section: Resultsmentioning

confidence: 99%

Kinetics of styrylquinolinc formation

Lynch

Gordon

1972

Journal of Heterocyclic Chem

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A comprehensive kinetic investigation of reactions occurring in the formation of styryl‐quinolines has been conducted. Specific rate data such as rate equations, rate constants, and thermodynamic activation values have been determined and utilized in a study of which factors are of greatest importance in the reactions forming 2‐styrylquinolines. A mechanism has been proposed for the condensation reaction which agrees with rate relationships found. Gas‐liquid partition chromatography was used to follow the kinetics of the condensation reactions. A rate constant of 5.41 × 10−2M−1min−1 was found for the reaction of benzaldehyde with 2‐methyl‐quinoline using zinc chloride as a catalyst at 104.0°. Rate constants of 1.28 × 10−2 MT−1 min−1 and 1.05 × 10−2 M−1 min−1 were found for the reactions of p‐methylbenzaldehyde and p‐methoxybenzaldehyde with quinaldine to form 2‐(p‐methylstyryl)quinoline and 2‐(p‐methoxystyryl)‐quinoline, respectively at 92.4°. A linear relationship was found using the Hammett equation. An Arrhenius plot was constructed from rate constants determined at five different temperatures for the reaction of benzaldehyde and quinaldine to form 2‐styrylquinoline, using zinc chloride as a catalyst. The energy of activation, Ea, was found to be 22.2 kcal/mole for this reaction. The enthalpy of activation, ΔH‡, free energy of activation, ΔF‡, and entropy of activation, ΔS‡, were found to be 21.4 kcal/mole, 27.7 kcal/mole and ‐16.7 eu/mole, respectively, at 104.0°. The mechanism proposed in the formation of 2‐styrylquinoline involves the fast formation of a carbanion‐zinc chloride complex, which then attacks, in the rate determining step, the aldehyde utilized in the reaction. The lack of reaction of certain methylquinolines is attributed to the inadequacy of the carbanion formed and not to the difficulty involved in the initial formation of the carbanion.

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Section: Resultsmentioning

confidence: 99%

Kinetics of styrylquinolinc formation

Lynch

Gordon

1972

Journal of Heterocyclic Chem

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“…Of the two common calibration methods-Le., direct calibration and calibration by internal standard (8,9,28,29)-0dy the latter will eliminate the effect of random sample variation for a single trial. This is evident from a comparison of coefficients of variation, V , for a single trial in Table I (direct calibration) where it is about 3.6%, and in Table I1 (internal stand- I n the determination of absolute amounts of components by either method, systematic sample error b is eliminated, provided the same preset injection volume is used throughout (cf.…”

Section: Discussionmentioning

confidence: 99%

Quantitative Analysis of Submicrogram Amounts of High Boiling Compounds by Flame Ionization Gas Liquid Chromatography.

Vandenheuvel¹

1963

Anal. Chem.

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“…Normalized per cent of peak area was used to calculate the weight fraction of each component as recommended by Rosie and Grob (1957).…”

Section: Methodsmentioning

confidence: 99%

Oligomerization of 1-Butene in Sulfuric Acid. Mechanisms and Rates

Naworski¹,

Harriott²

1969

Ind. Eng. Chem. Fund.

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The oligomerizstion of liquid 1 -butene catalyzed by concentrated sulfuric acid was studied in an adiabatic, capillary-flow reactor at 17.5" and 25" C. The reaction products were analyzed by gas-liquid chromatography. The maior products were 5-methyl-2-heptene, 5-methyl-1 -heptene, 2,2-dimethyl-3-hexene, and 5-methyl-3-heptene. Butene cgnsumption rates were calculated from axial temperature profiles measured by thermistors. The reaction rates per unit area of the butene drops were 0.98 X lod3 g. mole/ (min.)(sq. cm.) at 17.5" C. and 1.07 X

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Thermal Conductivity Behavior. Importance in Quantitative Gas Chromatography

Cited by 82 publications

References 15 publications

Kinetics of styrylquinolinc formation

Kinetics of styrylquinolinc formation

Quantitative Analysis of Submicrogram Amounts of High Boiling Compounds by Flame Ionization Gas Liquid Chromatography.

Oligomerization of 1-Butene in Sulfuric Acid. Mechanisms and Rates

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