Computerized analysis and correction of differential scanning calorimetric data for effects due to thermal lag and heat capacity changes

Heuvel, H. M.; Lind, K. C. J. B.

doi:10.1021/ac60291a005

Cited by 56 publications

(9 citation statements)

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“…One of the major problems in any temperature scanning technique is the presence of temperature gradients (thermal lag) in the sample. Detailed studies of the effect of thermal lag on the measurement of reaction enthalpy, heat capacities, and phase transition temperatures have been carried out (13)(14)(15)(16). The chief objective of the present work was to study the consequences of slow heat transfer in the sample.…”

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confidence: 99%

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Effect of thermal lag and measurement precision in differential scanning calorimetry: theoretical guidelines for enzyme-substrate reactions by the method of orthogonal collocation

Whiting

Carr²

1978

Anal. Chem.

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A simplified model of a differential scanning calorimeter (DSC) with large (40-120 pL) aqueous enzyme sample was simulated digitally by the mathematical technique called orthogonal collocation in order to observe the errors due to thermal lag (temperature and concentration gradients) in calculating the first-order Arrhenius kinetic parameters Zand AE. Only two dimensionless parameters were found to Influence the determinate errors in the data, one related to the scan rate and the other related to the rate of diffusion relative to the rate of chemical reaction. The errors were independent of AH, C", and Dm and also the parameters Z, AE, and T0 as long

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confidence: 99%

“…Figure13. Plot of relative error in dcv/df, (A); 1 -a, (B); d«/df/(1a), (C); and In k, (D) vs. alpha.…”

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confidence: 99%

Effect of thermal lag and measurement precision in differential scanning calorimetry: theoretical guidelines for enzyme-substrate reactions by the method of orthogonal collocation

Whiting

Carr²

1978

Anal. Chem.

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“…Many analytical forms of f [25][26][27][28] have been identified in the literature. For this study, the function f(a) chosen, consistent with Ref.…”

Section: Theoretical Aspectmentioning

confidence: 99%

Aquilanti–Mundim deformed Arrhenius model in solid-state reactions

Agreda

2016

J Therm Anal Calorim

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Although the theoretical framework supporting the use of non-extensive statistical theory for the study of chemical reaction kinetics and solid-state diffusive reactions is well established, direct evaluation of the parameters involved-such as the case of pair (d, e) appearing in the d-Arrhenius model-in the pertinent experimental data has yet to be generalized. This study proposes the use of ''d-Arrhenius log-log plots'' instead of Arrhenius semilog plots as a tool to determine the kinetic parameters of a reaction and their application to two different solid-state reactions obtained by DSC measurements in an Al-Fe-Si alloy. The paper goes on to show that the data obtained by DSC using the Arrhenius law generate a single k(T), whereas resorting to the Aquilanti-Mundim deformed Arrhenius model generates a set of (d, e) parameter pairs capable of reproducing the experimental data. Different (d, e) pairs generate different k(T) (d = 0, e = Q) corresponding to the Arrhenius pair. The effect of the different (d, e) pairs on the different functions related to the kinetics of the reaction is examined.Graphical Abstract AMDA graph showing linearity for different (d, e) pairs obtained from the precipitation reaction Guinier-Preston zones measured by DSC in an AA8011 commercial alloy (Superior) and Q activation energy for different pairs (bottom). The pair of Arrhenius (0, Q) in both graphs is represented by perpendicular and horizontal lines, respectively.

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“…Values of Cp to be substituted into Eq. (2) may be determined with sufficient accuracy from DSC ordinate displacements and scanning rates corrected for non-linearities in the temperature program [9,24]. Time constants, once known, allow correction of thermal lags, concerning either the ordinate displacement of DSC traces [9,10], or, on account of the relation between z and fiT, the abscissa temperature [5].…”

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confidence: 99%

“…The correction for thermal lag of measurements on DSC curves always requires knowledge of the filtering effects, either instrumental or not, that influence the shape of the curve itself [9,10,26].…”

Section: B) Relation Between the Parameters ~O And P And The Functionmentioning

confidence: 99%

Determination of some parameters to be utilized in correcting DSC curves for effects due to thermal lag

Vallebona¹

1979

Journal of Thermal Analysis

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Computerized analysis and correction of differential scanning calorimetric data for effects due to thermal lag and heat capacity changes

Cited by 56 publications

References 2 publications

Effect of thermal lag and measurement precision in differential scanning calorimetry: theoretical guidelines for enzyme-substrate reactions by the method of orthogonal collocation

Effect of thermal lag and measurement precision in differential scanning calorimetry: theoretical guidelines for enzyme-substrate reactions by the method of orthogonal collocation

Aquilanti–Mundim deformed Arrhenius model in solid-state reactions

Determination of some parameters to be utilized in correcting DSC curves for effects due to thermal lag

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