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**Isosteric enthalpies for hydrogen adsorbed on nanoporous materials at high pressures.** / Bimbo, Nuno; Sharpe, Jessica E.; Ting, Valeska P.; Noguera-Diaz, Antonio; Mays, Timothy J.

Research output: Contribution to journal › Journal article › peer-review

Bimbo, N, Sharpe, JE, Ting, VP, Noguera-Diaz, A & Mays, TJ 2014, 'Isosteric enthalpies for hydrogen adsorbed on nanoporous materials at high pressures', *Adsorption-Journal of the International Adsorption Society*, vol. 20, no. 2, pp. 373-384. https://doi.org/10.1007/s10450-013-9575-7

Bimbo, N., Sharpe, J. E., Ting, V. P., Noguera-Diaz, A., & Mays, T. J. (2014). Isosteric enthalpies for hydrogen adsorbed on nanoporous materials at high pressures. *Adsorption-Journal of the International Adsorption Society*, *20*(2), 373-384. https://doi.org/10.1007/s10450-013-9575-7

Bimbo N, Sharpe JE, Ting VP, Noguera-Diaz A, Mays TJ. Isosteric enthalpies for hydrogen adsorbed on nanoporous materials at high pressures. Adsorption-Journal of the International Adsorption Society. 2014 Feb;20(2):373-384. https://doi.org/10.1007/s10450-013-9575-7

@article{52ab8ff958aa495281870e35d8609dee,

title = "Isosteric enthalpies for hydrogen adsorbed on nanoporous materials at high pressures",

abstract = "A sound understanding of any sorption system requires an accurate determination of the enthalpy of adsorption. This is a fundamental thermodynamic quantity that can be determined from experimental sorption data and its correct calculation is extremely important for heat management in adsorptive gas storage applications. It is especially relevant for hydrogen storage, where porous adsorptive storage is regarded as a competing alternative to more mature storage methods such as liquid hydrogen and compressed gas. Among the most common methods to calculate isosteric enthalpies in the literature are the virial equation and the Clausius-Clapeyron equation. Both methods have drawbacks, for example, the arbitrary number of terms in the virial equation and the assumption of ideal gas behaviour in the Clausius-Clapeyron equation. Although some researchers have calculated isosteric enthalpies of adsorption using excess amounts adsorbed, it is arguably more relevant to applications and may also be more thermodynamically consistent to use absolute amounts adsorbed, since the Gibbs excess is a partition, not a thermodynamic phase. In this paper the isosteric enthalpies of adsorption are calculated using the virial, Clausius-Clapeyron and Clapeyron equations from hydrogen sorption data for two materials-activated carbon AX-21 and metal-organic framework MIL-101. It is shown for these two example materials that the Clausius-Clapeyron equation can only be used at low coverage, since hydrogen's behaviour deviates from ideal at high pressures. The use of the virial equation for isosteric enthalpies is shown to require care, since it is highly dependent on selecting an appropriate number of parameters. A systematic study on the use of different parameters for the virial was performed and it was shown that, for the AX-21 case, the Clausius-Clapeyron seems to give better approximations to the exact isosteric enthalpies calculated using the Clapeyron equation than the virial equation with 10 variable parameters.",

keywords = "Isosteric enthalpies of adsorption, Hydrogen storage, Thermal management, Storage systems, Porous materials, Physisorption, OBERFLACHEN INHOMOGENER AKTIVITAT, ADSORPTION VON GASGEMISCHEN, GIBBSIAN SURFACE EXCESS, SIZE DISTRIBUTION, GAS-ADSORPTION, PORE-SIZE, STORAGE, CARBON, ENERGY, HEAT",

author = "Nuno Bimbo and Sharpe, {Jessica E.} and Ting, {Valeska P.} and Antonio Noguera-Diaz and Mays, {Timothy J.}",

year = "2014",

month = feb,

doi = "10.1007/s10450-013-9575-7",

language = "English",

volume = "20",

pages = "373--384",

journal = "Adsorption-Journal of the International Adsorption Society",

issn = "0929-5607",

publisher = "Springer Netherlands",

number = "2",

}

TY - JOUR

T1 - Isosteric enthalpies for hydrogen adsorbed on nanoporous materials at high pressures

AU - Bimbo, Nuno

AU - Sharpe, Jessica E.

AU - Ting, Valeska P.

AU - Noguera-Diaz, Antonio

AU - Mays, Timothy J.

PY - 2014/2

Y1 - 2014/2

N2 - A sound understanding of any sorption system requires an accurate determination of the enthalpy of adsorption. This is a fundamental thermodynamic quantity that can be determined from experimental sorption data and its correct calculation is extremely important for heat management in adsorptive gas storage applications. It is especially relevant for hydrogen storage, where porous adsorptive storage is regarded as a competing alternative to more mature storage methods such as liquid hydrogen and compressed gas. Among the most common methods to calculate isosteric enthalpies in the literature are the virial equation and the Clausius-Clapeyron equation. Both methods have drawbacks, for example, the arbitrary number of terms in the virial equation and the assumption of ideal gas behaviour in the Clausius-Clapeyron equation. Although some researchers have calculated isosteric enthalpies of adsorption using excess amounts adsorbed, it is arguably more relevant to applications and may also be more thermodynamically consistent to use absolute amounts adsorbed, since the Gibbs excess is a partition, not a thermodynamic phase. In this paper the isosteric enthalpies of adsorption are calculated using the virial, Clausius-Clapeyron and Clapeyron equations from hydrogen sorption data for two materials-activated carbon AX-21 and metal-organic framework MIL-101. It is shown for these two example materials that the Clausius-Clapeyron equation can only be used at low coverage, since hydrogen's behaviour deviates from ideal at high pressures. The use of the virial equation for isosteric enthalpies is shown to require care, since it is highly dependent on selecting an appropriate number of parameters. A systematic study on the use of different parameters for the virial was performed and it was shown that, for the AX-21 case, the Clausius-Clapeyron seems to give better approximations to the exact isosteric enthalpies calculated using the Clapeyron equation than the virial equation with 10 variable parameters.

AB - A sound understanding of any sorption system requires an accurate determination of the enthalpy of adsorption. This is a fundamental thermodynamic quantity that can be determined from experimental sorption data and its correct calculation is extremely important for heat management in adsorptive gas storage applications. It is especially relevant for hydrogen storage, where porous adsorptive storage is regarded as a competing alternative to more mature storage methods such as liquid hydrogen and compressed gas. Among the most common methods to calculate isosteric enthalpies in the literature are the virial equation and the Clausius-Clapeyron equation. Both methods have drawbacks, for example, the arbitrary number of terms in the virial equation and the assumption of ideal gas behaviour in the Clausius-Clapeyron equation. Although some researchers have calculated isosteric enthalpies of adsorption using excess amounts adsorbed, it is arguably more relevant to applications and may also be more thermodynamically consistent to use absolute amounts adsorbed, since the Gibbs excess is a partition, not a thermodynamic phase. In this paper the isosteric enthalpies of adsorption are calculated using the virial, Clausius-Clapeyron and Clapeyron equations from hydrogen sorption data for two materials-activated carbon AX-21 and metal-organic framework MIL-101. It is shown for these two example materials that the Clausius-Clapeyron equation can only be used at low coverage, since hydrogen's behaviour deviates from ideal at high pressures. The use of the virial equation for isosteric enthalpies is shown to require care, since it is highly dependent on selecting an appropriate number of parameters. A systematic study on the use of different parameters for the virial was performed and it was shown that, for the AX-21 case, the Clausius-Clapeyron seems to give better approximations to the exact isosteric enthalpies calculated using the Clapeyron equation than the virial equation with 10 variable parameters.

KW - Isosteric enthalpies of adsorption

KW - Hydrogen storage

KW - Thermal management

KW - Storage systems

KW - Porous materials

KW - Physisorption

KW - OBERFLACHEN INHOMOGENER AKTIVITAT

KW - ADSORPTION VON GASGEMISCHEN

KW - GIBBSIAN SURFACE EXCESS

KW - SIZE DISTRIBUTION

KW - GAS-ADSORPTION

KW - PORE-SIZE

KW - STORAGE

KW - CARBON

KW - ENERGY

KW - HEAT

U2 - 10.1007/s10450-013-9575-7

DO - 10.1007/s10450-013-9575-7

M3 - Journal article

VL - 20

SP - 373

EP - 384

JO - Adsorption-Journal of the International Adsorption Society

JF - Adsorption-Journal of the International Adsorption Society

SN - 0929-5607

IS - 2

ER -