Mechanism of high-temperature CO2 sorption on lithium zirconate

Lithium zirconate (Li2ZrO3) is one of the most promising materials for CO2 separation from flue gas at high temperature. This material is known to be able to absorb a large amount of CO2 at around 400-700 degrees C. However, the mechanism of the CO2 sorption/desorption process on Li2ZrO3 is not known yet. In this study, we examined the CO2 sorption/desorption mechanism on Li2ZrO3 by analyzing the phase and microstructure change of Li2ZrO3 during the CO2 sorption/desorption process with the help of thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and X-ray diffraction (XRD) analyses. Li2ZrO3 powders were prepared from lithium carbonate (Li2CO3) and zirconium oxide (ZrO2) by the solid-state method, and the CO2 sorption/desorption property was examined by TGA. It was shown that pure Li2ZrO3 absorbs a large amount of CO2 at high temperature with a slow sorption rate. Addition of potassium carbonate (K2CO3) and Li2CO3 in the Li2ZrO3 remarkably improves the CO2 sorption rate of the Li2ZrO3 materials. DSC analysis for the CO2 sorption process indicates that doped lithium/potassium carbonate is in the liquid state during the CO2 sorption process and plays an important role in improving the CO2 uptake rate. XRD analysis for phase and structure change during the sorption/desorption process shows that the reaction between Li2ZrO3 and CO2 is reversible. Considering all data obtained in this study, we proposed a double-shell model to describe the mechanism of the CO2 sorption/desorption on both pure and modified Li2ZrO3.     

Physicochemical properties related to long-term phosphorus retention by drinking-water treatment residuals

Drinking-water treatment residuals (WTRs) are nonhazardous materials that can be obtained free-of-charge from drinking-water treatment plants to reduce soluble phosphorus (P) concentrations in poorly P sorbing soils. Phosphorus sorption capacities of WTRs can vary 1-2 orders of magnitude, on the basis of short-term equilibration times (up to 7 d), but studies dealing with long-term (weeks to months) P retention by WTRs are lacking. Properties that most affect long-term P sorption capacities are pertinent to the efficacy of WTRs as amendments to stabilize P in soils. This research addressed the long-term (up to 80 d) P sorption/desorption characteristics and kinetics for seven WTRs, including the influence of specific surface area (SSA), porosity, and total C content on the overall magnitude of P sorption by seven WTRs. The data confirm a strong but variable affinity for P by WTRs. Aluminum-based WTRs tended to have higher P sorption capacity than Fe-based WTRs. Phosphorus sorption with time was biphasic in nature for most samples and best fit to a second-order rate model. The P sorption rate dependency was strongly correlated with a hysteretic P desorption, consistent with kinetic limitations on P desorption from micropores. Oxalate-extractable Al + Fe concentrations of the WTRs did not effectively explain long-term (80 d) P sorption capacities of the WTRs. Micropore (CO2-based) SSAs were greater than BET-N2 SSAs for most WTRs, except those with the lowest (<80 g kg(-1)) total C content. There was a significant negative linear correlation between the total C content and the CO2/N2 SSA ratio. The data suggest that C in WTRs increases microporosity, but reduces P sorption per unit pore volume or surface area. Hence, variability in C content confounds direct relations among SSA, porosity, and P sorption. Total C, N2-based SSA, and CO2-based SSAs explained 82% of the variability in the long-term P sorption capacities of the WTRs. Prediction of long-term P sorption capacities for different WTRs may be achieved by taking into account the three proposed variables.     

Characterization of charcoal adsorption sites for aromatic compounds: insights drawn from single-solute and bi-solute competitive experiments

Charcoal, the residue of incomplete biomass burning that is found in many soils and sediments, is considered a high affinity sorbent for organic pollutants. However, little is known about the microscopic processes controlling sorption. The purpose of this study was to gain molecular-scale insight into the sorption on a charcoal of three weakly soluble aromatic compounds [benzene (BEN), toluene (TOL), and nitrobenzene (NBZ)] by conducting both single-solute and bi-solute experiments. The charcoal (420 m2 g(-1)) was produced from maple wood shavings by oxygen-limited pyrolysis at 673 K. Solute affinity for charcoal followed the order NBZ > TOL > BEN. Commonly employed sorption models did not adequately describe the single-solute isotherms. Competition in both TOL-BEN and the TOL-NBZ bi-solute systems was strong. Normalization of the isotherms for the hydrophobic driving force by using an existing free energy correlation between sorption and partitioning to an inert solvent (benzene or n-hexadecane) with a nonpolar aromatic compound calibration set resulted in a finding of enhanced sorption of NBZ relative to the coalesced BEN and TOL isotherms, indicating some specificity in the interaction of NBZ. The competitive data indicated 1:1 molar competition between BEN and TOL and between NBZ and TOL, showing conclusively that this specificity was not due to a subpopulation of sorption sites unique to NBZ. H-bonding was ruled out, as the relative affinity for the sorbent among the solutes did not change at all when increasing the solution pH from 6.5 to 11. 1H NMR experiments showed molecular complexation in chloroform between NBZ and model graphene polycyclic aromatic units (naphthalene, phenanthrene, and pyrene) which was absentfor BEN and TOL. This result, in combination with the results of a companion study (Zhu and Pignatello, Environ. Sci. Technol. (in press)), is used to support the existence of pi-pi electron donor-acceptor interactions between NBZ (electron acceptor) and the polycyclic aromatic charcoal surface (electron donor) as the cause of enhanced NBZ sorption.     

Critical evaluation of desorption phenomena of heavy metals from natural sediments

In natural sediments, the majority of heavy metal ions are generally associated with the solid phase. To become bioavailable, the metal ions must desorb from the solid. Numerous studies of heavy metals in sediments have suggested that sorption and desorption exhibit hysteresis (i.e., the two processes are not reversible), while other studies have suggested that desorption hysteresis does not exist. In this study, sorption/desorption hysteresis of lead (Pb) and cadmium (Cd) was evaluated over the following range of conditions: (i) desorption induced by replacing the supernatant liquid with contaminant-free electrolyte solution; (ii) desorption induced by lowering the solution pH with mineral acid; and (iii) desorption induced by sequestration with EDTA. Given the importance of dissolved organic and inorganic ligands in regulating heavy metal behavior in nature sediments, sorption/desorption experiments were conducted on both untreated and prewashed sediments. Prewashing treatment increases the sorption potential of Cd but not Pb. Desorption hysteresis is observed in both the untreated and the prewashed sediments using the replaced supernatant method, and the desorption hysteresis appears to increase with aging time. Hysteresis is not observed when desorption is initiated by lowering the solution pH. A large fraction of the sorbed heavy metal ions can be easily desorbed by EDTA; between 0.04 and 1.2 mmol/kg Cd and Pb ions are resistant to desorption.     

Moisture sorption characteristics of dried acid casein from buffalo skim milk

Adsorption and desorption isotherms of dried acid casein prepared from buffalo skim milk were determined at 25°, 35° and 45 °C over a water activity range of 0.11-0.97 using static moisture gain/loss from test samples. Both the adsorption and desorption isotherms exhibited sigmoid shape corresponding to type II, typical to many foods. There was generally a negative temperature effect on equilibrium moisture content. The effect of temperature was, however, statistically not significant over the temperature range of 25-45 °C. Of the seven sorption models tested for fitting the sorption data, the GAB model gave the best fit at all the three temperatures. The temperature dependence of GAB parameters has been determined in the form of Clausius-Clapeyron equation. The calculated values of monolayer moisture content from BET isotherm equation have been found to be lower than the corresponding values found by using GAB equation. However, in both cases the monolayer moisture was higher in desorption than the adsorption and deceased with increase in temperature. The net isosteric heat of sorption decreased exponentially with increasing moisture content and approached a constant value of 0.331 kJ/mol at moisture content 28 g/100 g (d.b.). The moisture sorption hysteresis observed at 25°, 35° and 45 C was statistically significant. The extent of hysteresis was negligible in monolayer moisture content region, occurred predominantly in the water activity range 0.35-0.60 and decreased at higher water activities. Total hysteresis energy was evaluated from the sorption data using Everett and Whitton plot. The effect of increase in temperature was to decrease the amount of hysteresis.     

On the reversibility of sorption to black carbon: distinguishing true hysteresis from artificial hysteresis caused by dilution of a competing adsorbate

Sorption hysteresis in environmental sorbents has important implications for pollutant transport and bioavailability. We examined the reversibility of sorption of benzene, toluene, and nitrobenzene, both singly and in pairs, by wood charcoal. A previous study showed that these compounds compete for the same set of adsorption sites on the char. Single-solute sorption was weakly hysteretic at high concentrations. The finding of comparable irreversibility for these compounds was taken as evidence that hysteresis is true and caused by pore elasticity. Hysteresis in the presence of a competitor was weak at low cosolute concentration but became stronger as the cosolute concentration increased. We attribute the growing hysteresis with cosolute concentration to a thermodynamic "competitor dilution effect"--a heretofore-unrecognized cause of hysteresis in multi-solute systems when the competing solute is simultaneously diluted with the target solute in the desorption step. It arises because the target solute re-equilibrates from a sorption point where competition is relatively high, to a desorption point where competition is relatively low. Simulations based on Ideal Adsorbed Solution Theory, a thermodynamic competition model, support the hypothesis. The cosolute also causes an increase in the linearity of the target solute isotherm, also attributable to competition thermodynamics. The competitive dilution effect can play a role in pollutant behavior in real systems if competing substances, natural or anthropogenic, are diluted or degraded making the target less accessible with time.     

Heat of sorption of water in dried fruits

The heats of moisture adsorption and desorption in four dried fruits (sultana raisins, figs, prunes and apricots) were estimated from equilibrium sorption data, using the Clausius-Clapeyron equation in the temperature range 15–60°C. The net isosteric heat of sorption ( q st) decreased sharply from about 20 kJ mol⁻¹ water to near zero when the moisture content was increased from 0.05 to 0.50kg water kg⁻¹ dry matter. An exponential function was fitted to the experimental q st values at various moisture contents (X) , yielding two characteristic constants ( q 0 and X 0) for each fruit. Mean and total heats of sorption were calculated from the proposed empirical equation, which are useful for enthalpy prediction in food dehydration. The heats of desorption were higher than the heats of adsorption, indicating significant hysteresis in the sorption of water, especially in dried apricots.     

Desorption kinetics of phenanthrene in aquifer material lacks hysteresis

Desorption experiments were carried out in flow through columns following long-term sorption batch experiments (up to 1010 days at 20 degrees C; Rügner, H.; Kleineidam, S.; Grathwohl, P. Long-term sorption kinetics of phenanthrene in aquifer materials. Environ. Sci. Technol. 1999, 33, 1645-1651) to elucidate sorption/desorption hysteresis phenomena of phenanthrene in aquifer materials. Most of the sorbents employed in this study (homogeneous lithocomponents separated from aquifer sediments or fresh rock fragments) showed highly nonlinear sorption isotherms because of coal particles embedded inside the grains. Because sorption capacities were high, sorption equilibrium was not reached in most of the sorbents during the initial sorptive uptake experiments lasting up to 1010 days. Desorption was studied up to 90 days at 20 degrees C. The temperature was raised after that stepwise from originally 20 to 30, 40, 50, and finally to 70 degrees C for selected samples to estimate activation energies of desorption. A numerical intraparticle pore diffusion model was used to fit sorptive uptake data and subsequently for pure forward prediction of the release rates in the desorption column experiments. Desorption was initially fast followed by extended tailing which in other studies is fitted by using multirate first-order models. Our results demonstrate that the retarded intraparticle pore diffusion model can predict the desorption rates with a single diffusion rate constant obtained independently from the long-term batch sorption experiment. No evidence for hysteresis was found, suggesting that many hysteresis phenomena reported earlier are experimental artifacts resulting from nonequilibrium effects and "nonphysical" models. The different temperature steps allowed one to additionally calculate activation energies of desorption (45-59 kJ mol(-1)), which were in reasonably good agreement with results from earlier studies for a retarded pore diffusion process. In addition, equilibrium sorption isotherms were determined at 20 and 40 degrees C to compare sorption and desorption enthalpies. Both were in good agreement, confirming that desorption was not significantly different from sorption.     

An isotope exchange technique to assess mechanisms of sorption hysteresis applied to naphthalene in kerogenous organic matter

The sorption of organic compounds to natural sorbents is often found to show hysteresis. The objective of this study was to develop an experimental technique based on the use of 14C isotopes to distinguish hysteresis due to experimental artifacts from true hysteresis due to thermodynamically irreversible processes. The study was also designed to investigate causation of true hysteresis (irreversible sorption). The technique determines the rates and the degree of isotope exchange (IE) on equilibrated sorption and desorption points at different constant bulk chemical concentrations. The technique was applied to the sorption of naphthalene (NAPH) on Beulah-Zap lignite, a low rank reference coal composed mainly of kerogen. Sorption of bulk was found to be reversible below 10(-5) g L(-1), but irreversible above 10(-4) g L(-1). Complete isotope exchange on sorption and desorption points that defined an irreversible cycle demonstrated that hysteresis was true. A comparison of normalized uptake and release kinetics of labeled and bulk NAPH at different concentrations revealed slow structural deformation processes of the sorbent during bulk sorption and desorption. This is taken as corroborating evidence for the pore deformation hypothesis of hysteresis in which incoming sorbate molecules induce quasi-reversible changes in the organic matter that lead to different pathways for sorption and desorption. Although unable to rule it out completely, the data demonstrate that physical entrapment of sorbate molecules plays a minor, if any, role to the observed hysteresis in this system.     

Thermodynamic Properties of Water on Rice as Calculated from Reversible and Irreversible Isotherms

Moisture sorption isotherms (MSI) of dehydrated rice obtained at 10°, 20°, and 30° for two successive adsorption and desorption cycles were used to compute thermodynamic functions of water on rice. Uncompensated heats declined with increasing temperature, from 41 J/g dry matter at 10°C to 5.6 J/g dry matter at 30°C. No hysteresis was observed in cycle 2 isotherms at any temperature, indicating thermodynamic reversibility. The cycle 2 MSI were generally in between the adsorption and desorption branches of the cycle 1 MSI. Behavior of the thermodynamic quantities calculated from cycle 2 MSI was qualitatively similar to those calculated from the cycle 1 adsorption MSI, though their magnitudes differed. Some implications of these results are discussed.     

Sorption/desorption reversibility of phenanthrene in soils and carbonaceous materials

Sorption/desorption of phenanthrene in two soil samples and carbonaceous materials was found to yield co-incident equilibrium isotherms and no significant hysteresis was observed. Additionally, release of native phenanthrene was investigated. Equilibrium sorption and desorption isotherms were determined using pulverized samples of Pahokee peat, lignite, and high-volatile bituminous coal, a mineral soil, and an anthropogenic soil. Instead of the conventional decant-and-refill batch method, sorption/desorption was driven by temperature changes using consistent samples. Sorption started at 77 degrees C and was increased by reducing the temperature stepwise to 46, 20, and finally 4 degrees C. For desorption the temperature was increased stepwise again until 77 degrees C was reached. Besides the co-incident sorption and desorption isotherms at each temperature step, the solubility-normalized sorption/desorption isotherms of all different temperatures collapseto unique overall isotherms. Leaching of native phenanthrene occurred at much lower concentrations but was well predicted by extrapolation of the spiked sorption isotherms indicating that the release of native phenanthrene involves the same sorption/desorption mechanisms as those for newly added phenanthrene.     

Synthesis and CO₂ adsorption properties of molecularly imprinted adsorbents

A series of molecularly imprinted adsorbents of CO(2) were developed by molecular self-assembly procedures, using ethanedioic acid, acrylamide, and ethylene glycol dimethacrylate as template, functional monomer, and cross-linker, respectively. Textural properties of these adsorbents were characterized by N(2) adsorption experiment, thermo-gravimetric analysis, and Fourier transform infrared spectroscopy. CO(2) adsorption capacities of adsorbents were investigated by thermo-gravimetric balance under 15% CO(2)/85% Ar atmosphere. Adsorption selectivity of CO(2) was studied by fixed-bed adsorption/desorption experiments. All the adsorbents displayed good thermal stability at 200 °C. Among them, MIP1b, with the higher amine content, exhibited the largest CO(2) capacity, which maintained steady after 50 adsorption-desorption cycles. Although MIP3 showed the highest specific surface, the CO(2) capacity was lower than that of MIP1b. CO(2) adsorption mechanism of molecularly imprinted adsorbents was determined to be physical sorption according to the adsorption enthalpies integrated from the DSC heatflow profiles. The calculated separation factors of CO(2) under 15% CO(2)/85% N(2) atmosphere were above 100 for all adsorbents.     

Equilibrium moisture content and heat of sorption of Gelidium sesquipedale

Moisture equilibrium data for adsorption and desorption of water from Gelidium sesquipedale were investigated at temperatures in the range of 30-50°C and water activity ranging from 0.05 to 0.9. The experimental procedure used was based on the gravimetric static method. The sorption curves of Gelidium sesquipedale decreased with increase in temperature at constant relative humidity. The hysteresis effect was observed. The experimental data of sorption were described by six models. The GAB and modified BET models were found to be the most suitable for describing the sorption curves. The isosteric heats of desorption and adsorption of water were determined from the equilibrium data at different temperatures.     

High-temperature drying of scots pine. A comparison between HT- and LT-drying

In order to study the influence of high temperature on wood properties, boards from Scots pine were dried at three different schedules, two high-temperature-schedules (HT) and one at low temperature (LT). Strength properties as hardness, cleavage- and shear-strength were determined and sorption/desorption behaviour were studied. Material was analysed concerning carbohydrate and extractive content and mould growth test at wooden surfaces. Results showed a significant influence of temperature on decreasing shear strength and equilibrium moisture content (EMC) in sorption/desorption tests. Sorption/desorption tests resulted in up to 2.4% lower EMC for HT dried material at the same climate compared with LT-dried and the hysteresis effect seems to be more pronounced in HT-dried material. Mould growth test showed an inhibiting effect of HT-drying on mould susceptibility at wooden surfaces. Carbohydrate analysis revealed a lower content of hemicelluloses in HT-dried boards which indicates a decomposition of the hemicelluloses explaining the decrease in shear strength and hygroskopic moisture uptake seen in the HT dried boards.     

NMR characterization of 13C-benzene sorbed to natural and prepared charcoals

We investigated how the NMR properties of uniformly 13C-labeled benzene molecules are influenced by sorption to charcoals produced in the laboratory and collected from the field following wildfires. Uniformly 13C-labeled benzene was sorbed to two charcoals produced in the laboratory at 450 and 850 degrees C. The chemical shift of benzene sorbed to the higher-temperature charcoal was 5-6 ppm lower than that of benzene sorbed to the lower-temperature charcoal. This difference was attributed to stronger diamagnetic ring currents (which cause a shift to lower ppm values) in the more condensed or "graphitic" high-temperature charcoal. The chemical shift of benzene sorbed to two charcoals collected from the field following wildfires indicated a degree of charcoal graphitization intermediate between that of the two laboratory-prepared charcoals. Variable contact time and dipolar dephasing experiments showed that the molecular mobility of sorbed benzene molecules increased with increasing charcoal graphitization, and also increased with increasing benzene concentration. We propose that the chemical shift displacement of molecules sorbed to charcoal could be used to identify molecules sorbed to black carbon in heterogeneous matrixes such as soils and sediments, and to establish how condensed or "graphitic" the black carbon is.     

Water sorption by proteins: milk and whey proteins

The content and physical state of water in foods influence their physical, chemical, quality, safety, and functional behavior. Information concerning the sorption behavior of dairy proteins, in the water activity (Aw) range 0 to 0.9, is collated in this paper. The sorption behavior of proteins in general, the kinetics of absorption, factors affecting water binding, the phenomenon of desorption hysteresis, and the chemical and physical nature of water/protein interactions are reviewed in general terms. This is followed by a discussion of thermodynamic aspects of sorption phenomena and the adequacy of the various equations for describing sorption isotherms of proteins. After a discussion of the methods available for measuring sorption by milk proteins, the sorption behavior of various milk protein preparations, i.e., nonfat dry milk, whey proteins, caseins, and milk powders is summarized. Finally, the water activity of cheese and its relationship to solute mobility and solvent water are discussed. Some of the unique features of protein behavior, i.e., conformational changes, swelling, and solubilization are cited as possible sources of disparities between various reports.     

Development of engineered natural organic sorbents for environmental applications. 2. Sorption characteristics and capacities with respect to phenanthrene

The effects of superheated water processing on enhancement of phenanthrene sorption by various source materials of natural organic matter (NOM) were systematically examined. Sorption capacities and subsequent phenanthrene retention characteristics of all organic materials tested were markedly increased by superheated water processing. Temperature effects on enhancement of the sorption behaviors of the test materials were greater than those of processing time, moisture content, and the presence of mineral catalysts. Greatest enhancement was observed for processing at 250 degrees C for 5 h with a moisture content of 50%. Strong correlations of sorption capacities and isotherm nonlinearities with processing temperature, and with the atomic ratios of oxygen to carbon (O/C), aromaticity, and hydrophobicity of the processed materials were observed. The sorption/desorption hysteresis indices of the processed materials also increased linearly with processing temperatures and O/C ratios. This is consistent with our observations of increased condensation and aromatization of NOM during superheated water processing presented in the first paper of this series. The relationships described provide direct experimental evidence that the sorption-desorption properties of NOM geosorbents are closely related to their degree of aromatization and condensation, and the work suggests strong potential for production of efficient and cost-effective engineered natural organic sorbents for environmental applications.     

Effect of Water Activity and Moisture Content on the Stability of Beet Powder Pigments

The effect of water activity (“dry”– 0.84) and moisture content on the stability of beet pigments (betanine and vulgaxanthine I) was investigated in beet powder stored at 35°C. Pigment deterioration followed a first order reaction. Water activity and moisture content had a pronounced exponential effect on pigment stability. A decrease of approximately one order of magnitude in pigment stability was observed when a_w was increased from 0.32 to 0.75. Storing the powder at a_w of 0.12 or below resulted in practically no deterioration of the pigments over a period of several months. Profound differences in pigment stability were attributed to sorption hysteresis and system composition.     

Diffusion coefficients of water and organic volatiles in carbohydrate-water systems

Summary. The diffusion coefficients of water, D _w, and acetone, D _a, in aqueous solutions of malto-dextrin have been determined over a range of moisture contents of the malto-dextrin above 10%. At a few selected moisture contents, the diffusion coefficients of ethyl acetate, benzene, carbon tetrachloride, camphor and methane have also been determined. Diffusion coefficients were derived from measurements of sorption and desorption by a malto-dextrin layer.
The diffusion coefficient was found to be dependent on both the moisture contents and the size of the diffusing molecule. Over the range of moisture contents investigated, log D _w was found to be proportional to C _w-1 and log D_a proportional to C _w-1/2, where C _w is the concentration of water (kg/m³) in the malto-dextrin. For the compounds studied, the logarithm of the diffusion coefficient measured at a moisture content of 20.1% was found to be approximately proportional to the molecular 'diameter' of the diffusant.
This knowledge helps to explain the phenomenon of flavour retention during the drying of liquid foods.     

Sorption and conformational characteristics of reconstituted plant cuticular waxes on montmorillonite

Plant cuticular waxes are essential barriers that regulate the transport of water and organic molecules to intact cuticular membranes. They also compose a significant fraction ofthe recalcitrant aliphatic components of soil organic matter (SOM). In this study, we examined the sorption and desorption of three polycyclic aromatic hydrocarbons (PAHs), naphthalene (NAPH), phenanthrene (PHEN), and pyrene (PYR), by cuticular waxes of green pepper (Capsicum annuum) that had been reconstituted by loading them onto montmorillonite (at four different loadings). The reconstituted wax samples, with and without sorbed PAHs, were characterized by solid-state 13C NMR to supply the evidence of melting transition. The sorption isotherms fit well to a Freundlich equation. Sorption isotherms were practically linear except for that of PYR sorption to the low-load wax-montmorillonite sample. The organic-carbon-normalized sorption coefficients (Koc) depended on PAH's lipophilicity (e.g., octanol-water partition coefficient) and increased with increasing wax-load on clay. Desorption was dependent on PAH's molecular sizes and sorbed amounts and on the wax load of the clay. Desorption hysteresis was observed only at high loads of NAPH and PHEN, and it decreased with both increasing wax load and molecular size (i.e. NAPH > PHEN > PYR). Contributing to hysteresis, the melting transition of the reconstituted waxes after sorbing the PAHs was confirmed by solid-state 13C NMR data. Upon adsorption, the intensity of the NMR peak at 29 ppm (attributed to mobile amorphous paraffinic domains) increased, and a peak at 167 ppm (-COOH) appeared, reflecting the transition of solid amorphous to mobile amorphous domains in the reconstituted waxes. The intensity of melting induced by PAH adsorption decreased with increasing PAH molecular size.