The swelling of charcoal. Part III. Experiments with the lower alcohols

Abstract

When a rod of well-baked wood charcoal contained in an extensometer is plunged into methyl alcohol, a noise like the quenching of hot iron is produced, and the moving parts of the extensometer are violently disturbed, as by a sudden impact. Though such effects are to be classed as irreversible and even irreproducible (where the charcoal is visibly fractured), quantitative investigation shows the expansion phenomenon to be no more inherently so than are the effects which accompany the admission of gas to an evacuated vessel. There can be no doubt that the primary factor determining the violence of the effect is the ability of the adsorbed molecules to spread over the surface of the charcoal, not (as has been suggested by analogy with other systems) in a series of infrequent jumps, but with great rapidity. With increase of molecular weight of the alcohol, the effect becomes less violent, especially if only one end of the charcoal is immersed in the liquid; but in none of the systems so far examined has a time-lag been found between adsorption and expansion. Granted the free mobility of a fraction of the molecules forming the adsorbed phase on charcoal, mere economy of hypothesis demands that one should enquire, before making ad hoc assumptions as to the nature of the charcoal surface, whether or not the phenomena are quantitatively similar to the better understood effects which occur at the surfaces of liquids; the present communication records an attempt to provide an answer to this question by appeal to experiments carried out with a series of adsorbates of closely related constitution. On the basis of the results described in this and in earlier papers, it can be asserted without hesitation that the two sets of phenomena do in fact run parallel to a remarkable degree. No doubt remains that the expansion actually provides a measure of the lowering of the surface energy of the charcoal mass; this is comprehensible, so far as when wood is carbonized the tendency of the carbon to reduce its surface energy to a minimum must be a primary cause of its shrinkage, and must determine, among other factors, the extent to which this shrinkage takes place. Further, a direct comparison of our expansion data with those for the lowering of the surface tension of mercury by the vapours of the same alcohols brings to light so many points of resemblance as to indicate a similarity of mechanism in the two cases. No evidence whatever was found in favour of the view (of which one of the present authors was an original advocate) that the swelling is a lattice distortional effect caused by sessile adsorbed molecules; and though the investigation of other systems may reveal the existence of an expansion effect where the molecular motions are confined to isolated areas of low potential (and so make it necessary ultimately to reconcile the two conflicting viewpoints), such a development is not foreshadowed in the data here presented.

Adsorption-induced deformation of nanoporous materials—A review

“…Based on a series of experiments, [71][72][73][74] which all showed monotonic expansion of charcoal samples with increased adsorbate pressure, Bangham concluded that the measured linear strain is proportional to the decrease in the surface energy c of a solid, caused by adsorption…”

Deformation of Microporous Carbons during N2, Ar, and CO2 Adsorption: Insight from the Density Functional Theory

“…In this work we focus on the origin of adsorption-induced deformation of microporous carbons. Typically microporous materials, such as carbons or zeolites, exhibit a nonmonotonic adsorption-induced deformation: they contract at low stages of micropore filling and switch to expansion as adsorption progresses. − The extent of observed contraction and expansion depends on the structure of the adsorbent, , the adsorptive applied, ,,,− and the temperature. ,,, The first model for adsorption-induced deformation of microporous materials was proposed by Bangham, who considered the energy change of the adsorbate–adsorbent interface to be the sole source of stress within the porous structure . This concept was later implemented into the framework of Biot’s poromechanics by the use of the Gibbs adsorption equation. ,, However, the fundamental issue of this approach is that adsorption leads to a reduction of the interfacial energy, and thereby only expansion should be observed, in clear contradiction with experimental findings.…”

Monte Carlo Simulation of Adsorption-Induced Deformation in Finite Graphitic Slit Pores

“…An early experimental investigation by Meehan in 1927 reported the expansion of charcoal on adsorption of carbon dioxide . Later the expansion of charcoal upon exposure to water vapor, ammonia, alcohols, and other gases was studied by Bangham and co-workers, − and the deformation of carbon rods was investigated by Flood and co-workers in the 50s and 60s, − who found evidence of contraction at low pressures. Adsorption-induced deformation was also investigated for materials other than carbon, − and both expansion and contraction were recorded.…”