MineraLosical JouRNaL, VoL. 22, No.1, pp. 1-10, JaNuary 2000 Hydration enthalpies of inorganic porous materials with different structures Masaya Suzukr*, Fumihiko Ouasut*, Keiichi INUKar*, Masaki MaeDA*, Shinji Tomura* and Tadato Mizora* * National Industrial research institute of Nagoya, AIST, MITI, Nagoya 462-8510, Japan ** Department of Advanced Materials Science and Engineering, Faculty of Engineering, Yam- aguchi University, Ube 755-8611, Japan Abstract ‘The hydration enthalpies of three inorganic porous materials (sepiolite, MCM41_ and synthesized allophane) were measured by means of the adiabatic vapor absorption calorime- ter. The average hydration enthalpy (-AMY,) were in the order, allophane (-57k3/mol) < sepio: lite (-54K0/mol) < MCMAl (-49kJ/mol) when the samples were hydrated for 10 minutes in the calorimeter, after dehydration in vacuum at 100°C. Samples with smaller pore radius give the larger absolute values of the hydration enthalpy (-AM,). The -AM, values of sepiolite inereased with dehydration temperature and decreased with hydration duration, whereas that of MCM4I remained almost constant regardless of dehydration temperature and hydration duration. The hydration rates for these samples were large in the early stage, but quickly lost the rate. The hydration state of the porous materials with large voids is concluded being simi- lar to that of free water. Introduction The porous materials excel in abilities of gas-absorption and/or ion exchange, and are used practically in various fields such as catalysts, absorbents and ion exchangers. In particu- lar, zeolites are used as absorbents, builder and catalyzer in petrochemistry, because they have the interesting characters for absorption ability, the distribution of pore size, strong slope of, electric field and molecular sieving. In spite of such variety of above mentioned functions of microporous materials, there are few applications focusing on water molecules as a main con- stituent of the materials. Tchernev (1978) made ice using a solar energy by a system of water- zeolite pair for the heat exchange. Mizota (1999) succeeded in making ice using hot water by the heat pump system. Maier-Laxhuber et al. (1983) reported that in the experiment of using 800kg of zeolite, the temperature achieved from -5°C to 96°C on the condition of the capacity of heat storage of 900MI (250kWh). They reported that this system generates I0kW of con- denser output on the 26kW of electricity input for dehydrated stage and 30kW output at the maximum cooling stage. Recently a humidity self contro! material has also been developed by using the porous materials (Tomura er al., 1998; Maeda er al, 1998).2 M. SuzUKI, F. OHASHI, K. INUKAl, M, MAEDA, S. ToMURA and T. MizoTa ‘Tchernev (1980) evaluated the heat pump system by using the hydration enthalpy val- ues of natural zeolites such as chabasite and clinoptilotte, and discussed the efficiency of the system by the instantaneous efficiency defined as AH,/AH, (evaporation enthalpy of water divided by evaporation enthalpy of zeolitic water). Kasai et al. (1994) and Mizota et al. (1995) measured the hydration enthalpies of synthetic A-type, cation-exchanged-A-type and some natural zeolites, and discussed about the ability of heat exchange from the total heat of hydration Q defined as dehydration energy per one kilogram of hydrated zeolite. In the present study we measured the hydration enthalpies of inorganic porous materi- als, such as sepiolite, MCMAI and synthesized allophane. The hydration enthalpies of zeo- lite, cordierite, and so on (lohnson et al., 1982; Carey et al, 1992), but those of sepiolite, MCM41 and allophane haven't measured yet. These materials are characterized by different structures from zeolites and have the larger pore size distribution. Sepiolite has 0.67x1.34nm sized pores characterized by tunnel-shaped pores from the crystal structure and an ideal for- mula: MggSi;2039(OH),(OH2),: (H0)s. MCM41 (Mesoporous Crystalline Materials-41) has tunnel pores of about 4-8nm diameter and a formula: SiO,. Allophane has a hollow spherical structure with a Snm outer diameter and 3nm inner diameter, and about 0.4nm sized micropore in the crust of allophane. It has general formula: 1.0-2.0SiO3 - Al;O3--2.5- 3.0H0. The correlation between pore size distributions and hydration enthalpies of these three materials was discussed. Our results are compared with the results obtained in A-type zeolite (Mizota et al, 1995), Experimental Sample, synthetic method and estimation of pore size Sepiolite from Turkey and Spain (Oumi Kogyo Co. Brown, and Mizusawa Kagaku Co. SP, respectively) were used for the present work. Two kinds of MCM4I with different pore size were prepared according to the method of Ohashi et al. (1999). The fumed amorphous silica was dissolved into sodium hydroxide solution and stirred for 1 h. 25wt% of individual aqueous suspensions of decyl-(n=10) and hexadecyl-(n=16)trimethylammonium chloride were prepared. After the solution, were mixed and stirred for 1h, the resulting homogeneous sol was held in a reaction cell for 7 days at 100°C. The products were washed with distilled water and dried at 40°C. The material was heated successively at 600°C for 6 h under air flow, in order to remove the organic template. ‘Two kinds of allophane with the different pore size distribution were synthesized by the rapid mixing method (Ohashi et al, 1997). A solution of aluminium chloride were mixed with a sodium orthosilicate-NaOH solution of 30mM (=30mmoV/)) and 100mM to give Si/Al molar ratio of 0.6 for preparing “allophane 30mM” and “allophane 100mM”, respectively. Each solution was agitated for I h and then filtrated to collect the precursor. The solid was then dispersed into distilled water and afterwards heated at 80°C for 5 days in a reaction cell. ‘The product formed was collected by filtration, washed with distilled water and dried at 40°C to obtain allophane samples.Hydration enthalpies of inorganic porous materials with different structures 3 ‘TaBLe 1. Pore radii, specific surface areas, and absorbed water amounts at two different vapor pressures for three kinds of microporous materials. PIP Riom Sim?-gt 01 Wad Sepiolite (Turkish) 09 8 218 507 2802 Sepiolite (Spanish 0910-11 257 585 2383 MCMAI (n=10) 2 965 093 50.52 MCMAI (n=16) 32 1344 047 86.92 Allophane (30M) 22 02) 490 838 5287 Allophane (100m) 29 02) 552 8637845 ‘R: pore radius, S:lig:N>-BET specific surface area, Way : water amount absorbed, iP: relative pressure. Pore radii indicated in parentheses for allophane as O.2nm are quoted from Henmi (1991), ‘The specific surface area and pore size distribution were measured by liq-No-BET ‘method, (Sorptomatic 1900, Carlo Erba Instruments Co.). Powder samples were heated at 100°C in vacuum for 2 h before measurements. The pore size distribution under Inm for sepi- lite were calculated by the Kelvin’s equation, based on data from the differential thermo- gravimetory (RTG320U, Seiko Electron Co.) (Tomura et al., 1998). The amount of absorbed water was measured by means of an absorption isotherm analyzer (EAM-O1S, Tokyo Shikenki Manufacturing Co.) with 0.1-0.5g of powdered sample evacuated at 25°C for sev- eral hours. The results of specific surface area, pore radius and absorbed water are shown in Table 1. Sepiolite has two kinds of pore sizes; 0.9nm sized pores (micropore) characterized by tunnel-shaped pores from the crystal structure, and about 10nm sized pores (mesopore) as interstices among sepiolite-fibers. Allophane has also two kinds of pore sizes. The specif- ic surface area and TEM observation show that the synthetic allophane has a hollow spheri- cal structure with a Snm outer diameter and 3nm inner diameter. Although we have no ‘means to measure the smaller pore size distribution below 0.5nm, those of micropore in the crust of allophane is quoted from Henmi, et al, (1991) in Table 1 to be 0.2nm in parentheses, Other larger 2-3nm sized pores should be assigned to interstices among allophane particles. Hydration calorimetry Heat of water-vapor absorption was measured by means of the adiabatic vapor absorp- tion calorimeter at 23-25°C (Kasai, et al., 1994; Mizota, et al., 1998). A glass flask contain- ing about 0.25g sample was connected to an evacuation system with a greaseless valve and a joint. The flask was then evacuated and heated at various temperatures for I h for the dehy- ration of sample. After dehydration the flask with sample was transferred to the calorime- ter. The calorimeter system was evacuated first to remove air remained. Water vapor was introduced through a glass tube to the sample from the water reservoir at a fixed time, and the temperature elevation by hydration was measured. Relations between temperature eleva- tion and supplied electric energy were used to calibrate water-absorption energy for the4 M. SuzUKI, F. OHASHI, K. INUKAl, M, MAEDA, S. TomURA and T. Mizora calorimetry. The amount of dehydration was obtained from the difference before and after the dehydration by correcting air weight evacuated. The amount of hydration was obtained from the weight-difference before and after the hydration. Results ‘Characterization of porous materials The results of specific surface area, pore radius and absorbed water are shown in Table 1. Sepiolite has two kinds of pore sizes; 0.9nm sized pores (micropore) characterized by tun- nel-shaped pores from the crystal structure, and about 10nm sized pores (mesopore) as inter- stices among sepiolite-fibers. Allophane has also two kinds of pore sizes. The specific sur- face area and TEM observation show that the synthetic allophane has a hollow spherical structure, Although we have no means to measure the smaller pore size distribution below 0.5nm, those of micropore in the crust of allophane is quoted from Henmi, et al. (1991) in Table I to be 0.2nm in parentheses. Other larger 2-3nm sized pores should be assigned to interstices among allophane particles. Hydration enthalpy Hydration enthalpy used in the present paper indicates a integrated molar enthalpy obtained as an average from a whole hydration process in the calorimetric measurement: AHy = Gp lim, where AH, gn and my are hydration enthalpy, heat of hydration and molar amount of water hydrated, respectively. Amount of dehydration (Wa), amount of hydration (W,) and hydration enthalpy (AH) were shown in Table 2 for porous materials dehydrated at various tempera- tures. Hydration duration (time lengths for which the sample was exposed under the vapor pressure of free water) other than 10 minutes was shown next to the dehydration temperature in Table 2. As the hydration heat (the hydration enthalpy) is exothermic and thus negative, each hydration enthalpy was shown as the positive value like -AMf, in the present paper. The -AH, values of the sepiolite from Turkey and Spain were determined to have 54.0 1.5kJ/mol and 54.140.5kI/mol, respectively, when they had been dehydrated at 100°C and hydrated for 10 min, The -AFy value increased with dehydration temperature. The -AH values for MCM&4I samples of n=10 and n=16 showed 50. 11.5kI/mol and 48.4#1.0k3/mol, respectively, after dehydration at 100°C and the hydration time for 10 min. These value were almost constant independent of dehydration temperatures for both of them. The -AH, value of the allophane increased with dehydration temperature, and showed 56.1:+2.0kJ/mol and 58.742.0kJ/mol for allophane 30mM and 100mM, respectively, when they were dehy- drated at 100°C and hydrated for 10 min. The -AM, value of the allophane was the maxi- mum of three samples. Relations between hydration enthalpies (AH) and the dehydration temperature (fg) is shown in Fig.l. Mg2*-exchanged A-type zeolites (Mg-A) is also shown in Fig. 1 for compati- son (Mizota er al., 1995). The -AH, value of sepiolite allophane and the zeolite increased with dehydration temperature, The value at 180°C is by 2-6kI/mol greater than that at 60°C. On theHydration enthalpies of inorganic porous materials with different structures 5 ‘Taste 2, Dehydration and hydration amounts (W and Wp) and vapor-hydration enthalpy (Ay) for porous materials dehydrated at various temperatures (fg) determined by means Of the adiabatic vapor hydration calorimeter. Hydration duration are specified in paren- theses, other Sepiolite Turkish) ‘Sepiolite (Spanish) MCMAT ( MCMAT ( Allophane(30mM ) “Allophane(100mM) for 10min. Talc 0 100 100(20min) 100(30min) 100¢60min) 140 180 60, 100 100 (20min) 100 GOmin) 100 (60min) 140 180 60 100 100 (60min) 140 180 60 100 100 (60min) 140 180 60, 100 140 180 60 100 140 180 m0 10.09 526 10.10 540 10.16 527 13.63 Sis 1757 sia 1001 56.7 1118 516 10.75 S21 9.76 54.1 11.08 527 12.26 S18 13.70 31 10.03 56.7 8.30 50.4 10.92 505 1083 305 2045 50.7 9.83 502 12.46 485 1147 48.0 1227 48.7 1435 494 1254 475 8.07 48.2 73.05 35.1 15.32 56.1 15.84 56.6 15.67 519 1424 37.0 1535 58.7 185 505 14.69 605 oe Zeolite) ae Alphane( tom) a SopitteySpanish) A= Alephane(somW) 8 Sepioto(Tursh) =e MoMarin=10) Ae MoMatin=t6) Fic, 1. Relations between hydra tion enthalpies (-AM) and the ‘dehydration temperature (3)6 M. Suzi, F. OHASHI, K. INUKAI, M, MAEDA, S. TOMURA and T. MizoTa 88 A 1 Sepiotte Turkish) 56 ® Sopioite (Spanish) % 54 2 2 52 = 7 50 48 a 76 25 3040 50 60 70 Hydration Duration / min Fic, 2. Relations between hydration enthalpies (-AH) andthe hydration duration «0 4 | [1 SepioiterTanisny 55 4 | | m sepiiterspaish) 5 o (© MoMst(n=10) E . © mowar(n=t6) 2m 0 2 ° 4 Alophane(3onM) ZS le ‘A Alophane(100m) 45 wf 4 “34 5 6 7 68 § Absorbed Water / wt% (PIP, =0.1) Fic. 3. Relations between hydration enthalpies (-AH) and amounts of absorbed water other hand, the values of MCM41 were kept almost constant regardless of dehydration temper- atures. Relations between hydration enthalpies and hydration duration are shown in Fig. 2. The -AH, value of sepiolite showed an slight decrease from 54kH/mol to 51ki/mol with increasing hydration duration. The -AH, value of MCM41 were however almost unchanged, Relations between hydration enthalpies and amounts of absorbed water is shown in Fig. 3 at the relative ‘vapor pressure of P/Po=0.1. The -AMf, showed larger value in materials of more absorbed water at PIP(=0.1Hydration enthalpies of inorganic porous materials with different structures 7 a Seer) ra oman acer en aan 200 : 100} ABS" * | pee IRE a ‘Hydration Duration / sec Rene ae a ee 35 Taree 3F 8 MCM41(n=10) ° —é- Allophane(30mM) ees 2 ~~ Zeolte(M-A) Ss 3 i 5 £ & 2 ° 100 200 300 400 500 0 Hydration Duration / sec FRc. 5. Change of vapor hydration rate with hydration duration progres. Hydration rate Relations between hydration heat (-g) and hydration duration (fy) are shown for various microporous materials dehydrated at 100°C (Fig. 4). The hydration heat was normalized to 1g of each sample. The value of allophane is the largest of all samples until 600s. The heat for the zeolite increased linearly with hydration duration. On the other hand, Igl-fy curve of sepiolite, MCM41 and allophane showed downward bending (Fig. 4). This indicates that the hydration of such materials reached saturation in relatively short time in comparison with that for zeolite. Rate of hydration was evaluated by differentiating Igi with #, as shown in Fig. 5. The rate for zeolite was rather constant regardless of hydration time, although rate8 M. SUZUKI, F. OHASHI, K. INUKAl, M. MAEDA, S. TomURA and T. Mizora values of other samples were large in the early stage. Discussion Correlation between -AH and pore radius The absolute value of the hydration enthalpy for microporous materials concerned in the present work seems to be increased with amounts of absorbed water at P/P)=0.1 as seen in Fig. 3, but the fact is explained due to the pore size differences among them. Clausius- Clapeyron equation expresses the relation between hydration enthalpy and vapor pressure: InP = AHy/RT-+ const a where P is the vapor pressure. A lower vapor pressure gives a larger absolute value of the hydration enthalpy for absorbents. The relation between vapor pressure and pore radius of porous materials is written as the Kelvin’s capillary condensation equation: In(PIPo) = -r4 RT 2V y cos Q where Po, nV,yand @ are respectively, saturated vapor pressure at the temperature T, pore radius, molar volume of water, surface tension and contacting angle. The equation reveals, that a smaller pore radius gives a lower vapor pressure for porous materials. The combina- tion of equations (1) and (2) suggests that the smaller voids in a microporous material gives the larger absolute value of the hydration enthalpy. The -AMj, values determined from mate- rials dehydrated at 100°C and hydrated for 10min, are shown as the following order: allophane (about 57kI/mol) > sepiolite (about 54kJ/mol) > MCMA1 (about 49ki/mol). ‘The pore radius of the same materials were in the order : allophane (about 0.2nm) < sepiolite (about 0.9nm) < MCM4I (about 2nm). As allophane and sepiolite consist of several different-sized pores in themselves, the smaller pore radius in average gives then the higher absolute value of the hydration enthalpy. The -AH}, value of mordenite is smaller by 5-10k3/mol than that of A-type zeolite, and the smaller -A, values indicate that the large cavities in mordenite composed of 12- ‘membered rings allow looser accumulation of water molecules than those in the smaller cavities of A-type zeolites composed of 8-rings (Mizota, et al., 1995). The present results confirmed this for microporous materials other than zeolites. Hydration state and behavior in porous material ‘The -AHy, value of sepiolite was decreased with hydration duration, but that of MCM41 was almost constant regardless of hydration duration (Fig. 2). In early stage of the absorp- tion, the water molecules will be absorbed first inside of the tunnel pores of about 0.9nm diameter in the crystal structure. After the smaller pores are filled with water, the larger pores such as interstices among fibers of sepiolite are stuffed successively. This explains the fact that the -AH}, value of sepiolite decreases apparently at the early stage of the hydration. For MCM4I, the weak absorption with the smaller -AH, of water molecules continuesHydration enthalpies of inorganic porous materials with different structures 9 24, $$ =O Zeca) 2 Mor) —& Mophano(somN) ea eo MoMatio=t0) + ‘A Aophane(toomi) ee > |S Seviotertnshy Ze “e Momsrin=16) 1 “a Sopote(Spanih) 2 10 Ey 100 140 160 220 tal°C Fic. 6. Relations between dehydration amounts (Wg) and the dehydration temperature ({4) through the whole stage of hydration. Relations between dehydration amounts and dehydration temperature were shown in Fig. 6. The dehydration rate of zeolite and allophane show an increase with dehydration temperature, but that of sepiolite slight increases, and MCM&4I almost constant, regardless of dehydration temperature. The dehydration rate depends on the dehydration temperature for these porous materials with radii of around 0.2nm, but those with about 1.0nm radius or the more are independent or nearly independent on the temperature. Differences in dehydra- tion rates of microporous materials are classified into two categories. Materials such as zeo- lite or allophane, which have smaller pore radii of the range of 0.2nm, is characterized by the zeolitic water and the dehydration rate depends on the temperature. The zeolitic water means water molecules bonded rather directly to oxygens of silicate framework or hydrated to exchangeable cations. Water molecules in the larger pore of the radius range of 1-3nm are. however those of the physisorption state or the capillary condensation. The energy for the dehydration of zeolite and allophane is thus larger than that for sepiolite and MCM4I. Ener- getic results obtained in the present work proved therefore that the water in the crust of allo- phane is in the state similar to that of the zeolitic water. ‘The hydration rate may be used as an indicator of the energetic gradation of absorbed water, The hydration rate of zeolite was almost constant regardless of hydration time, but those of other samples were large in their early stage and became gradually smaller (Fig. 5). A-type zeolite, which has very high crystallinity and almost same energetic state of the ‘water molecule, shows the large hydration speed, which is nearly constant. The hydration for the larger pore size materials shows relatively fast hydration rate in the early stage where ‘water was absorbed onto the surface inside-wall of the pore, but suddenly drops the rate due10 ‘M. SUZUKI, F. OHASHI, K. INUKAl, M. MAEDA, S. ToMURA and T, MiZOTA to multi-layer condensation of water molecules. 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