scholarly journals Gas adsorption and desorption effects on cylinders and their importance for long-term gas records

2015 ◽  
Vol 8 (12) ◽  
pp. 5289-5299 ◽  
Author(s):  
M. C. Leuenberger ◽  
M. F. Schibig ◽  
P. Nyfeler
Keyword(s):  
Mole Fraction ◽  
Pressure Dependence ◽  
Gas Adsorption ◽  
Binding Energies ◽  
Adsorption Model ◽  
Climate Chamber ◽  
Temperature Coefficients ◽  
Monolayer Adsorption ◽  
Pressure Changes ◽  
Adsorption Desorption

Abstract. It is well known that gases adsorb on many surfaces, in particular metal surfaces. There are two main forms responsible for these effects (i) physisorption and (ii) chemisorption. Physisorption is associated with lower binding energies in the order of 1–10 kJ mol−1, compared to chemisorption which ranges from 100 to 1000 kJ mol−1. Furthermore, chemisorption only forms monolayers, contrasting physisorption that can form multilayer adsorption. The reverse process is called desorption and follows similar mathematical laws; however, it can be influenced by hysteresis effects. In the present experiment, we investigated the adsorption/desorption phenomena on three steel and three aluminium cylinders containing compressed air in our laboratory and under controlled conditions in a climate chamber, respectively. Our observations from completely decanting one steel and two aluminium cylinders are in agreement with the pressure dependence of physisorption for CO2, CH4, and H2O. The CO2 results for both cylinder types are in excellent agreement with the pressure dependence of a monolayer adsorption model. However, mole fraction changes due to adsorption on aluminium (< 0.05 and 0 ppm for CO2 and H2O) were significantly lower than on steel (< 0.41 ppm and about < 2.5 ppm, respectively). The CO2 amount adsorbed (5.8 × 1019 CO2 molecules) corresponds to about the fivefold monolayer adsorption, indicating that the effective surface exposed for adsorption is significantly larger than the geometric surface area. Adsorption/desorption effects were minimal for CH4 and for CO but require further attention since they were only studied on one aluminium cylinder with a very low mole fraction. In the climate chamber, the cylinders were exposed to temperatures between −10 and +50 °C to determine the corresponding temperature coefficients of adsorption. Again, we found distinctly different values for CO2, ranging from 0.0014 to 0.0184 ppm °C−1 for steel cylinders and −0.0002 to −0.0003 ppm °C−1 for aluminium cylinders. The reversed temperature dependence for aluminium cylinders points to significantly lower desorption energies than for steel cylinders and due to the small values, they might at least partly be influenced by temperature, permeation from/to sealing materials, and gas-consumption-induced pressure changes. Temperature coefficients for CH4, CO, and H2O adsorption were, within their error bands, insignificant. These results do indicate the need for careful selection and usage of gas cylinders for high-precision calibration purposes such as requested in trace gas applications.

scholarly journals Gas adsorption and desorption effects on cylinders and their importance for long-term gas records

2014 ◽  
Vol 14 (13) ◽  
pp. 19293-19314 ◽  
Author(s):  
M. C. Leuenberger ◽  
M. F. Schibig ◽  
P. Nyfeler
Keyword(s):  
Gas Adsorption ◽  
Binding Energies ◽  
Adsorption Model ◽  
Climate Chamber ◽  
Temperature Coefficients ◽  
Monolayer Adsorption ◽  
Gas Consumption ◽  
Pressure Changes ◽  
Adsorption Desorption

Abstract. It is well known that gases adsorb on many surfaces, in particular metal surfaces. There are two main forms responsible for these effects (i) physisorption and (ii) chemisorption. Physisorption is associated with lower binding energies in the order of 1–10 kJ mol−1 compared to chemisorption ranging from 100 to 1000 kJ mol−1. Furthermore, chemisorption forms only monolayers, contrasting physisorption that can form multilayer adsorption. The reverse process is called desorption and follows similar mathematical laws, however, it can be influenced by hysteresis effects. In the present experiment we investigated the adsorption/desorption phenomena on three steel and three aluminium cylinders containing compressed air in our laboratory and under controlled conditions in a climate chamber, respectively. We proved the pressure effect on physisorption for CO2, CH4 and H2O by decanting a steel and an aluminium cylinder completely. The results are in excellent agreement with a monolayer adsorption model for both cylinders. However, adsorption on aluminium (0.3 ppm and 0 ppm for CO2 and H2O) was about 20 times less than on steel (6 ppm and 30 ppm, respectively). In the climate chamber the cylinders were exposed to temperatures between −10 to +50 °C to determine the corresponding temperature coefficients of adsorption. Again, we found distinctly different values for CO2 ranging from 0.0011 to 0.0133 ppm °C−1 for steel cylinders and −0.0003 to −0.0005 ppm °C−1 for aluminium cylinders. The reversed temperature dependence for aluminium cylinders is most probably due to temperature and gas consumption induced pressure changes. After correction, aluminium cylinders showed no temperature independence. Temperature coefficients for CH4, CO and H2O adsorption were, within their error bands, insignificant. These results do indicate the need for careful selection and usage of gas cylinders for high precision calibration purposes such as requested in trace gas applications.

scholarly journals Gas adsorption and desorption effects on cylinders and their importance for long-term gas records

2015 ◽  
Vol 8 (8) ◽  
pp. 8083-8112
Author(s):  
M. C. Leuenberger ◽  
M. F. Schibig ◽  
P. Nyfeler
Keyword(s):  
Gas Adsorption ◽  
Binding Energies ◽  
Adsorption Model ◽  
Climate Chamber ◽  
Temperature Coefficients ◽  
Monolayer Adsorption ◽  
Gas Consumption ◽  
Pressure Changes ◽  
Adsorption Desorption

Abstract. It is well known that gases adsorb on many surfaces, in particular metal surfaces. There are two main forms responsible for these effects (i) physisorption and (ii) chemisorption. Physisorption is associated with lower binding energies in the order of 1–10 kJ mol−1 compared to chemisorption ranging from 100 to 1000 kJ mol−1. Furthermore, chemisorption forms only monolayers, contrasting physisorption that can form multilayer adsorption. The reverse process is called desorption and follows similar mathematical laws, however, it can be influenced by hysteresis effects. In the present experiment we investigated the adsorption/desorption phenomena on three steel and three aluminium cylinders containing compressed air in our laboratory and under controlled conditions in a climate chamber, respectively. We proved the pressure effect on physisorption for CO2, CH4 and H2O by decanting one steel and two aluminium cylinders completely. The CO2 results for both cylinders are in excellent agreement with the pressure dependence of a monolayer adsorption model. However, adsorption on aluminium (< 0.05 and 0 ppm for CO2 and H2O) was about 10 times less than on steel (< 0.41 ppm and about < 2.5 ppm, respectively). The CO2 amounts adsorbed (5.8 × 1019 CO2 molecules) corresponds to about the five-fold monolayer adsorption indicating that the effective surface exposed for adsorption is significantly larger than the geometric surface area. Adsorption/desorption effects were minimal for CH4 and for CO. However, the latter dependence requires further attention since it was only studied on one aluminium cylinder with a very low mole fraction. In the climate chamber the cylinders were exposed to temperatures between −10 and +50 °C to determine the corresponding temperature coefficients of adsorption. Again, we found distinctly different values for CO2 ranging from 0.0014 to 0.0184 ppm °C−1 for steel cylinders and −0.0002 to −0.0003 ppm °C−1 for aluminium cylinders. The reversed temperature dependence for aluminium cylinders point to significantly lower desorption energies than for steel cylinders and might at least partly be due to temperature and gas consumption induced pressure changes. Temperature coefficients for CH4, CO and H2O adsorption were, within their error bands, insignificant. These results do indicate the need for careful selection and usage of gas cylinders for high precision calibration purposes such as requested in trace gas applications.

scholarly journals Laser THz Emission Spectroscopy of Gas Adsorption-Desorption Dynamics in Tungsten Disulfide Nanosheets

2016 ◽  
Vol 14 (0) ◽  
pp. 78-82 ◽  
Author(s):  
Filchito Renee Bagsican ◽  
Iwao Kawayama ◽  
Hironaru Murakami ◽  
Masayoshi Tonouchi ◽  
Andrew Winchester ◽  
...  
Keyword(s):  
Emission Spectroscopy ◽  
Gas Adsorption ◽  
Tungsten Disulfide ◽  
Adsorption Desorption

scholarly journals Isosteric Heat of Single Gas Adsorption on an Energetically Homogeneous Adsorbent Surface

1996 ◽  
Vol 13 (2) ◽  
pp. 105-114 ◽  
Author(s):  
J.K. Garbacz ◽  
A. Kopkowfki ◽  
A. Dabrowski
Keyword(s):  
Gas Adsorption ◽  
Isosteric Heat ◽  
Model Parameters ◽  
Experimental Systems ◽  
Adsorbent Surface ◽  
Monolayer Adsorption

An expression for the isosteric heat of the partially mobile monolayer adsorption of a single gas on a homogeneous adsorbent surface has been derived. Optimization of the model parameters has been performed for selected experimental systems.

A Reduced Fuel Cell Stack Model for Control and Fault Diagnosis

2006 ◽  
Vol 3 (4) ◽  
pp. 384-388 ◽  
Author(s):  
Damiano Di Penta ◽  
Karim Bencherif ◽  
Michel Sorine ◽  
Qinghua Zhang
Keyword(s):  
Fuel Cell ◽  
Fault Diagnosis ◽  
Gas Adsorption ◽  
Carbon Monoxide Poisoning ◽  
Important Indicator ◽  
Fuel Cell Stack ◽  
Electrode Potentials ◽  
The Difference ◽  
Adsorption Desorption ◽  
Stack Model

This paper proposes a reduced fuel cell stack model for control and fault diagnosis which was validated with experimental data. Firstly, the electro-chemical phenomena are modeled based on a mechanism of gas adsorption/desorption on catalysts at the anode and at the cathode of the stack, including activation, diffusion, and carbon monoxide poisoning. The electrical voltage of a stack cell is then modeled by the difference between the two electrode potentials. A simplified thermal model of the fuel cell stack is also developed in order to take into account heat generation from reactions, heat transfers, and evaporation/condensation of water. Finally, the efficiency ratio is computed as a model output. It is used to evaluate the efficiency changes of the entire system, providing an important indicator for fault detection.

scholarly journals Study on Shale Adsorption Equation Based on Monolayer Adsorption, Multilayer Adsorption, and Capillary Condensation

2017 ◽  
Vol 2017 ◽  
pp. 1-11 ◽  
Author(s):  
Qing Chen ◽  
Yuanyuan Tian ◽  
Peng Li ◽  
Changhui Yan ◽  
Yu Pang ◽  
...  
Keyword(s):  
Adsorption Isotherm ◽  
Shale Gas ◽  
Size Structure ◽  
Capillary Condensation ◽  
Critical Role ◽  
Nitrogen Adsorption ◽  
Adsorption Model ◽  
Multilayer Adsorption ◽  
Nitrogen Adsorption Isotherm ◽  
Monolayer Adsorption

Shale gas is an effective gas resource all over the world. The evaluation of pore structure plays a critical role in exploring shale gas efficiently. Nitrogen adsorption experiment is one of the significant approaches to analyze pore size structure of shale. Shale is extremely heterogeneous due to component diversity and structure complexity. Therefore, adsorption isotherms for homogeneous adsorbents and empirical isotherms may not apply to shale. The shape of adsorption-desorption curve indicates that nitrogen adsorption on shale includes monolayer adsorption, multilayer adsorption, and capillary condensation. Usually, Langmuir isotherm is a monolayer adsorption model for ideal interfaces; BET (Brunauer, Emmett, Teller) adsorption isotherm is a multilayer adsorption model based on specific assumptions; Freundlich isotherm is an empirical equation widely applied in liquid phase adsorption. In this study, a new nitrogen adsorption isotherm is applied to simultaneously depict monolayer adsorption, multilayer adsorption, and capillary condensation, which provides more real and accurate representation of nitrogen adsorption on shale. In addition, parameters are discussed in relation to heat of adsorption which is relevant to the shape of the adsorption isotherm curve. The curve fitting results indicate that our new nitrogen adsorption isotherm can appropriately describe the whole process of nitrogen adsorption on shale.

scholarly journals Statistical Mechanical Model of Gas Adsorption in a Metal-Organic Framework Harboring a Rotaxane Molecular Shuttle

2020 ◽  
Author(s):  
Jonathan Carney ◽  
David Roundy ◽  
Cory M. Simon
Keyword(s):  
Mechanical Model ◽  
Gas Adsorption ◽  
Adsorption Properties ◽  
Temperature Sensitive ◽  
Adsorption Model ◽  
Adsorption Sites ◽  
Statistical Mechanical Model ◽  
Metal Organic ◽  
Statistical Mechanical ◽  
Molecular Shuttle

Metal-organic frameworks (MOFs) are modular and tunable nano-porous materials with applications in gas storage, separations, and sensing. Flexible/dynamic components that respond to adsorbed gas can give MOFs unique or enhanced adsorption properties. Here, we explore the adsorption properties that could be imparted to a MOF by a rotaxane molecular shuttle (RMS) in its pores. In the unit cell of an RMS-MOF, a macrocyclic wheel is mechanically interlocked with a strut of the MOF scaffold. The wheel shuttles between stations on the strut that are also gas adsorption sites. At a level of abstraction similar to the seminal Langmuir adsorption model, we pose and analyze a simple statistical mechanical model of gas adsorption in an RMS-MOF that accounts for (i) wheel/gas competition for sites on the strut and (ii) gas-induced changes in the configurational entropy of the shuttling wheel. We determine how the amount of gas adsorbed, position of the wheel, and differential energy of adsorption depend on temperature, pressure, and the interactions of the gas/wheel with the stations. Our model reveals that, compared to a rigid, Langmuir material, the chemistry of the RMS-MOF can be tuned to render gas adsorption more or less temperature-sensitive and to release more or less heat upon adsorption. The model also uncovers a non-monotonic relationship between the temperature and the position of the wheel if gas out-competes the wheel for its preferable station.

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