A sodium smectite (NaS) with a cation exchange capacity (CEC) of 1.08 mol kg−1 was intercalated with methyltributylammonium cation (MTBA+) with proportions equivalent to 0.2, 0.4, 0.6, 0.8 and 1.0 times the CEC. The contents of adsorbed water and intercalated
MTBA+ in the prepared organosmectites (OSs) were determined by using the differential thermal analysis (DTA) and thermogravimetry
(TG) curves. The adsorbed water of 8% in the NaS decreases greatly in OSs with the increase of the MTBA+ content and reduces to 2.0% for the 1.0 CEC sample. This explains the gradual change of the NaS from hydrophilic to hydrophobic
character. Thermal degradation of the intercalated MTBA+ in OSs occurs approximately between 250–450°C. The oxidation of the formed charcoal to CO2 occurs between 450–850°C. The intercalated MTBA+ content for each OS is obtained from both the TG and carbon analysis. The results do not agree exactly, but both the results
tend to increase by increasing initial content of the MTBA+ in solution.
Thermogravimetric (TG) and differential thermal analysis (DTA) curves of methyltributylammonium smectite (MTBAS), methyltrioctylammonium
smectite (MTOAS), and di(hydrogenatedtallow)dimethylammonium smectite (DHTDMAS), and also corresponding sodium smectite (NaS)
and tetraalkylammonium chlorides (TAAC) were determined. The TAACs was decomposed exactly by heating up to 500°C. The adsorbed
water content of 8.0% in the pure NaS was decreased down to 0.2% depending on the size of the non-polar alkyl groups in the
tetraalkylammonium cations (TAA+). The thermal degradation of the organic partition nanophase formed between 2:1 layers of smectite occurs between 250–500°C.
Activation energies (E) of the thermal degradations in the MTBAS, MTOAS and DHTDMAS are 13.4, 21.9, and 43.5 kJ mol−1, respectively. The E value increases by increasing of the interlayer spacing along a curve depending on the size of the alkyl groups in the TAA+.
The mineralogical composition of the Kütahya calcium bentonite (CaB) from Turkey was obtained as mass% of 60% calcium rich
smectite (CaS), 30% opal-CT (OCT), trace amount illite (I), and some non-clay impurities by using chemical analysis (CA),
X-ray diffraction (XRD), and thermal analysis (TG-DTA) data. The crystallinity, porosity, and surface area of the samples
heated between 25–1300°C for 2 h were examined by using XRD, TG, DTA and N2-adsorption-desorption data. The position of the 001 reflection which is the most characteristic for CaS does not affect from
heating between 25–600°C and then disappeared. The decrease in relative intensity (I/I0) from 1.0 to zero and the increase in full width at half-maximum peak height (FWHM) from 0.25 to 1.0° of the 001 reflection
show that the crystallinity of the CaS decreased continuously by rising the heating temperature from 25 to 900°C and then
collapsed. The most characteristic 101 reflection for opals intensifies greatly between 900 and 1100°C with the opal becoming
The total water content of the natural bentonite after dried at 25, 105 and 150°C for 48 h were determined as 8.8, 5.0 and
2.5%, respectively. The mass loss occurs between 25 and 400°C over two steps with the maximum rate at 80 and 150°C, respectively.
The exact distinction of the dehydration temperatures for the adsorbed water and interlayer water is seen almost impossible.
The temperature interval, maximum rate temperature, and mass loss during dehydroxylation are 400–800°C, 670°C and 4.6–5.0%,
respectively. The maximum rate temperatures for decrystallization and recrystallization are 980 and 1030°C, respectively.
The changes in specific micropore volume (Vmi), specific mesopore volume (Vme), specific surface area (S) were discussed according to the dehydration and dehydroxylation of the CaS. The Vmi, Vme and S reach to their maxima at around 400°C with the values of 0.045, 0.115 cm3 g−1 and 90 m2 g−1, respectively. The radii of mesopores for the bentonite heated at 400°C are distributed between 1–10 nm and intensified approximately
at 1.5 nm.
The specific micro- and mesopore volumes (V) of alumina compacts fired between 900 and 1250 °C for 2 h were determined from nitrogen adsorption/desorption data. The V value was taken as a sintering equilibrium parameter. An arbitrary sintering equilibrium constant (Ka) was estimated for each firing temperature by assuming Ka = (Vi − V)/V, where Vi is the largest value at 900 °C before sintering. Also, an arbitrary Gibbs energy (ΔGa°) of sintering was calculated for each temperature using the Ka value. The graph of ln Ka versus 1/T and ΔGa° versus T were plotted, and the real enthalpy (ΔH°) and the real entropy (ΔS°) of sintering were calculated from the slopes of the obtained straight lines, respectively. On the contrary, real ΔG° and K values were calculated using the real ΔH° and ΔS° values in the ΔG° = −RT lnK = 165814 − 124.7T relation in SI units.
A method has been purposed to calculate some of the thermodynamic quantities for the thermal deformation of a smectite without
using any basic thermodynamic data. The Hançılı (Keskin, Ankara, Turkey) bentonite containing a smectite of 88% by volume
was taken as material. Thermogravimetric (TG) and differential thermal analysis (DTA) curves of the sample were obtained.
Bentonite samples were heated at various temperatures between 25–900°C for the sufficient time (2 h) until to establish the
thermal deformation equilibrium.
Cation-exchange capacity (CEC) of heated samples was determined by using the methylene blue standard method. The CEC was used
as a variable of the equilibrium. An arbitrary equilibrium constant (Ka) was defined similar to chemical equilibrium constant and calculated for each temperature by using the corresponding CEC-value.
The arbitrary changes in Gibbs energy (ΔGa0) were calculated from Ka-values. The real change in enthalpy (ΔH0) and entropy (ΔS0) was calculated from the slopes of the lnK vs. 1/T and ΔG vs. T plots, respectively. The real changes in Gibbs energy (ΔG0) and real equilibrium constant (K) were calculated by using the ΔH0 and ΔS0 values. The results at the two different temperature intervals are summarized as below: ΔG10=ΔH10−ΔS10T=−RTlnK1=47000−53t, (200–450°C), and ΔG20=ΔH20-ΔS20T=−RTlnK2=132000−164T, (500–800°C).
A model was proposed to calculate some thermodynamic parameters for the acid dissolution process of a bentonite containing
a calcium-rich smectite as clay mineral along with quartz, opal and feldspar as impurities. The bentonite sample was treated
with H2SO4 by applying dry method in the temperature range 50–150°C for 24 h. The acid content in the dry bentonite-sulphuric acid mixture
was 45 mass%. The total content (x) of Al2O3, Fe2O3 and MgO remained in the undissolved sample after treatment was taken as an equilibrium parameter. An apparent equilibrium
constant, Ka, was calculated for each temperature by assuming Ka=(xm−x)/x where xm is the total oxide content of the natural bentonite. Also, an apparent change in Gibbs free energy, ΔGao, was calculated for each temperature by using the Ka value. The graphs of lnKavs. 1/T and ΔGaovs. T were drawn and then the real change in both the enthalpy, ΔHo and the entropy, ΔSo, values were calculated from the slopes of the straight lines, respectively. Inversely, real ΔGo and K values were calculated from the real ΔHo and ΔSo values through ΔGo = −RT ln K = ΔHo − TΔSo equation. The best ΔHo and ΔSo fittings to this relation were found to be 65687 J mol−1 and 164 J mol−1K−1, respectively.
Authors:H. Bayram, M. Önal, G. Üstünışık, and Y. Sarıkaya
An industrial raw material taken from Sivrihisar (Eskişehir, Turkey) region was heat-treated at different temperatures in
the range of 100–1000�C for 2 h. The volumetric percentage of the particles having a diameter below 2 μm after staying in
an aqueous suspension of the material was determined as 67% by the particle size distribution analysis. The mineralogical
composition of the material was obtained as mass% of 32% palygorskite, 10% metahalloysite, 35% magnesite, 20% dolomite and
3% interparticle water by using the acid treatment, X-ray diffraction and thermal analysis (TG, DTA) data.
The temperature ranges were determined for the endothermic dehydrations for the interparticle water as 25–140�C, for the zeolitic
water as 140–320�C, and for the bound water as 320–480�C, in the palygorskite. The temperature range for the endothermic dehydroxylation
and exothermic recrystalization of the palygorskite is 780–840�C. The temperature range for the endothermic dehydroxylation
of the metahalloysite and calcinations of magnesite are coincided at 480–600�C. Dolomite calcined in the temperature range
of 600–1000�C by two steps. The zig-zag changes in the specific surface area (S/m2 g−1) and specific micro and mesopore volume (V/cm3 g−1) as the temperature increases were discussed according to the dehydrations in the palygorkskite, dehydroxylation of palygorskite
and metahalloysite, and calcinations in magnesite and dolomite.
Authors:Enver Ozan, A. Kükner, L. Canpolat, H. Öner, M.R. Gezen, S. Yilmaz, and S. Ozan
In this study, rats were made to inhale cigarette smoke in a specifically prepared container for different periods. The lung tissue samples of the subjects were examined by light microscopy, transmission electron microscopy (TEM) and scanning electron microscopy (SEM). Malonaldehyde, one of the free oxygen radicals was determined in lungs and plasma. The catalase activity level of erythrocyte and arginase levels were determined. Three groups were formed. The rats in the Ist and IInd groups were made to inhale cigarette smoke for 30 and 60 minutes a day for a total period of 3 months. Control group, the rats in the IIIrd group (controls) were made to inhale clean air during the same periods. An increase in the number of macrophages was observed in the pulmonary tissue of the exposed groups. Especially in the group that inhaled the smoke for long periods, the number of macrophages and the inclusion bodies contained in them increased. These differences could easily be observed in TEM studies. In the light microscopy and SEM observations, it arouse attention that the alveolar macrophages occurred as sets and their activation increased. Depending on the length of the exposure to cigarette smoke, an increase in the number of macrophages was observed. Statistically significant increases were determined in the malonaldehyde levels of pulmonary tissue and plasma when compared to the control group. Besides significant increases were found in the catalase activity levels of erythrocytes in the experimental groups.