• Title/Summary/Keyword: thermodynamic analysis

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Hydrogeochemical Research on the Characteristic of Chemical Weathering in a Granitic Gatchment (水文化學的 資料를 통한 花崗岩質 流域의 化學的 風化特性에 關한 硏究)

  • Park, Soo-Jin
    • Journal of the Korean Geographical Society
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    • v.28 no.1
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    • pp.1-15
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    • 1993
  • This research aims to investigate some respects of chemical weathering processes, espcially the amount of solute leaching, formation of clay minerals, and the chemical weathering rate of granite rocks under present climatic conditions. For this purpose, I investigated geochemical mass balance in a small catchment and the mineralogical composition of weathered bedrocks including clay mineral assemblages at four res-pective sites along one slope. The geochemical mass blance for major elements of rock forming minerals was calculated from precipitation and streamwater data which are measured every week for one year. The study area is a climatically and litholo-gically homogeneous small catchment($3.62Km^2$)in Anyang-shi, Kyounggi-do, Korea. The be-drock of this area id Anyang Granite which is composed of coarse-giained, pink-colored miner-als. Main rock forming minerals are quartz, K-Feldspar, albite, and muscovite. One of the chracteristics of this granite rock is that its amount of Ca and Mg is much lower than other granite rock. The leaching pattern in the weathering profiles is in close reltion to the geochemical mass balance. Therefore the removal or accumulation of dissolved materials shows weathering patterns of granite in the Korean peninsula. Oversupplied ions into the drainage basin were $H^+$, $K^+$, Fe, and Mn, whereas $Na^2+$, $Mg^2+$, $Ca^2+$, Si, Al and $HCO-3^{-}$ were removed from the basin by the stream. The consumption of hydrogen ion in the catchment implies the hydrolysis of minerals. The surplus of $K^+$ reflects that vegetation is in the aggravation stage, and the nutrient cycle of the forest in study area did not reach a stable state. And it can be also presumed that the accumulation of $K^+$ in the top soil is related to the surplus of $K^+$. Oversupplied Fe and Mn were presumed to accumulate in soil by forming metallic oxide and hydroxide. In the opposite, the removal of $Na^+$, Si, Al resulted from the chemical weathering of albite and biotite, and the amount of removal of $Na^+$, Si, Al reflected the weathering rate of the bedrock. But $Ca^2+$ and $Mg^2+$ in stream water were contaminated by the scattered calcareous structures over the surface. Kaolinite is a stable clay mineral under the present environment by the thermodynamical analysis of the hydrogeochemical data and Tardy's Re value. But this result was quite different from the real assemblage of clay miner-als in soil and weathered bedrock. This differ-ence can be explained by the microenvironment in the weathering profile and the seasonal variation of climatic factors. There are different clay forming environments in the stydy area and these differences originate from the seasonal variation of climate, especially the flushing rate in the weathering profile. As it can be known from the results of the analysis of thermodynamic stability and characteristics of geochemical mas balance, the climate during winter and fall, when it is characterized by the low flushing rate and high solute influx, shows the environmental characteristics to from 2:1 clay minerals, such as illite, smectite, vermiculite and mixed layer clay minerals which are formed by neoformation or transformation from the primary or secondary minerals. During the summer and spring periods, kaoli-nite is a stable forming mineral. However it should consider that the other clay minerals can transformed into kaolinite or other clay minerals, because these periods have a high flushing rte and temperature. Materials which are directly regulated by chemical weathering in the weathered bedrock are $Na^+$, Si, and Al. The leaching of Al is, however, highly restricted and used to form a clay mineral, and that of Si falls under the same category. $Na^+$ is not taked up by growing veget ation, and fixed in the weathering profile by forming secondary minerals. Therefore the budget of $Na^+$ is a good indicator for the chemical weathering rate in the study area. The amount of chemical weathering of granite rocks was about 31.31g/$m^2+$/year based on $Na^+$ estimation.

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Efficiency of Poultry Manure Biochar for Stabilization of Metals in Contaminated Soil (계분 바이오차를 이용한 토양 중금속 안정화 효율 평가)

  • Lim, Jung Eun;Lee, Sang Soo;Ok, Yong Sik
    • Journal of Applied Biological Chemistry
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    • v.58 no.1
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    • pp.39-50
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    • 2015
  • Stabilization of heavy metals such as Pb, Cd, Zn, and Cu was evaluated in contaminated soil treated with poultry manure (PM) as well as its biochars pyrolyzed at $300^{\circ}C$ (PBC300) and $700^{\circ}C$ (PBC700) at the application rates of 2.5, 5.0, and 10.0 wt% along with the control, prior to 21-days incubation. After incubation, soil pH was increased from 6.94 (control) to 7.51, 7.24, and 7.88 in soils treated with PM 10 wt%, PBC300 10 wt%, and PBC700 10 wt% treatments, respectively, mainly due to alkalinity of treatments. In the soil treated with PM, the concentrations of the toxicity characteristic leaching procedure (TCLP)-extractable Pb, Cd, Zn, and Cu were increased by up to 408, 77, 24, and 955%, respectively, compared to the control. These increases may possibly be associated with an increased dissolved organic carbon concentration by the PM addition. However, in the soil treated with PBC700, TCLP-extractable Pb, Cd, Zn, and Cu concentrations were reduced by up to 23, 38, 52, and 36%, respectively, compared to the control. Thermodynamic modelling using the visual MINTEQ was done to predict the precipitations of $Pb(OH)_2$, $Cu(OH)_2$ and P-containing minerals, such as chloropyromorphite [$Pb_5(PO_4)_3Cl$] and hydroxypyromorphite [$Pb_5(PO_4)_3OH$], in the PBC700 10 wt% treated soil. The SEM-elemental dot mapping analysis further confirmed the presence of Pb-phosphate species via dot mapping of PBC700 treated soil. These results indicate that the reduction of Pb concentration in the PBC700 treated soil is related to the formations of chloropyromorphite and hydroxypyromorphite which have very low solubility.

Smile Rearrangement of Herbicidal Flazasulfuron (제초성 Flazasulfuron의 Smile 자리옮김 반응)

  • Lee, Gwnag-Jae;Kim, Yong-Jip;Kim, Dae-Whang;Sung, Nack-Do
    • Applied Biological Chemistry
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    • v.39 no.1
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    • pp.70-76
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    • 1996
  • A series of the herbicidal pyridylsulfonyl areas, none substitutent, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(2-pyridylsulfonyl) urea, 3 and 3-trifluoromethyl substitutent, 1-(4,6-dimethoxypyrimidine-2-yl)-3-(3-trifluoromethyl-2-pyridylsulfonyl) urea, 5(Flazasulfuron) were synthesizied and the rate of hydrolysis of their has been studied in 25%(v/v) aqueous dioxane at $45^{\circ}C$. From the results of solvent effect($m{\ll}1,\;n{\ll}3\;&\;{\mid}m{\mid}{\ll}{\mid}{\ell}{\mid}$), thermodynamic parameter (${\Delta}S^{\neq}=0.54{\sim}\;-2.19\;e.u.\;&\;{\Delta}H^{\neq}=0.025\;Kcal.mol.^{-1}$), hydrolysis product analysis, $pK_a$ constant(3: 4.9 & 5: lit.4.6) and the rate equation, a marked difference in the kinetics of the reaction of 3 and 5(Flazasulfuron) was observed. It may be concluded that the hydrolysis of 5 proceeds through the $A-S_N2Ar$ reaction via conjugate acid$(5H^+)$ below pH 7.0, whereas, above pH 9.0, the hydrolysis proceeds through irreversibly $(E_1)_{anion}$ and reversibly $(E_1CB)_R$ mechanism via conjugate base(CB), respectively. But in case of 5, $A-S_N2Ar,\;(E_1)anion\;and\;(E_1CB)_R$ mechanism involved Smile rearrangement. The mate of rearrangement of 5 to a 3-trifluoromethyl-2-pyridylpyrimidinyl urea(PPU) in acid and 3-trifluoromethyl-2-pyridyl-4.6-dimethoxypyridinyl amine (PPA) in base was increased about 3.5 times by the introduction of trifluoromethyl group in the 3-position on the 2-pyridyl ring. From the basis of these findings, a possible mechanism for the hydrolysis of 5 was proposed and discussed.

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Comparative Study on the Estimation of CO2 absorption Equilibrium in Methanol using PC-SAFT equation of state and Two-model approach. (메탄올의 이산화탄소 흡수평형 추산에 대한 PC-SAFT모델식과 Two-model approach 모델식의 비교연구)

  • Noh, Jaehyun;Park, Hoey Kyung;Kim, Dongsun;Cho, Jungho
    • Journal of the Korea Academia-Industrial cooperation Society
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    • v.18 no.10
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    • pp.136-152
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    • 2017
  • The thermodynamic models, PC-SAFT (Perturbed-Chain Statistical Associated Fluid Theory) state equation and the Two-model approach liquid activity coefficient model NRTL (Non Random Two Liquid) + Henry + Peng-Robinson, for modeling the Rectisol process using methanol aqueous solution as the $CO_2$ removal solvent were compared. In addition, to determine the new binary interaction parameters of the PC-SAFT state equations and the Henry's constant of the two-model approach, absorption equilibrium experiments between carbon dioxide and methanol at 273.25K and 262.35K were carried out and regression analysis was performed. The accuracy of the newly determined parameters was verified through the regression results of the experimental data. These model equations and validated parameters were used to model the carbon dioxide removal process. In the case of using the two-model approach, the methanol solvent flow rate required to remove 99.00% of $CO_2$ was estimated to be approximately 43.72% higher, the cooling water consumption in the distillation tower was 39.22% higher, and the steam consumption was 43.09% higher than that using PC-SAFT EOS. In conclusion, the Rectisol process operating under high pressure was designed to be larger than that using the PC-SAFT state equation when modeled using the liquid activity coefficient model equation with Henry's relation. For this reason, if the quantity of low-solubility gas components dissolved in a liquid at a constant temperature is proportional to the partial pressure of the gas phase, the carbon dioxide with high solubility in methanol does not predict the absorption characteristics between methanol and carbon dioxide.

Mobility of Transition Metals by Change of Redox Condition in Dump Tailings from the Dukum Mine, Korea (덕음광산 광미의 산화${\cdot}$환원 조건에 따른 전이원소의 이동성)

  • 문용희;문희수;박영석;문지원;송윤구;이종천
    • Economic and Environmental Geology
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    • v.36 no.4
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    • pp.285-293
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    • 2003
  • Tailings of Dukum mine in the vadose and saturated zone were investigated to reveal the mobility of metal elements and the condition of mineralogical solubility according to redox environments throughout the geochemical analysis, thermodynamic modelling, and mineralogical study for solid-samples and water samples(vadose zone; distilled water: tailings=5 : 1 reacted, saturated zone; pore-water extracted). In the vadose zone, sulfide oxidation has generated low-pH(2.72∼6.91) condition and high concentration levels of S $O_4$$^{2-}$(561∼1430mg/L) and other metals(Zn : 0.12∼l57 mg/L, Pb : 0.06∼0.83 mg/L, Cd : 0.06∼l.35 mg/L). Jarosite$(KFe_3(SO_4)_2(OH)_6)$ and gypsum$(CaSO_4{\cdot}2H_2O$) were identified on XRD patterns and thermodynamics modelling. In the saturated zone, concentration of metal ions decreased because pH values were neutral(7.25∼8.10). But Fe and Mn susceptible to redox potential increased by low-pe values(7.40∼3.40) as the depth increased. Rhodochrosite$(MnCO_3)$ identified by XRD and thermodynamics modelling suggested that $Mn^{4+}$ or $Mn^{3+}$ was reduced to $Mn^{2+}$. Along pH conditions, concentrations of dissolved metal ions has been most abundant in vadose zone throughout borehole samples. It was observed that pH had more effect on metal solubilities than redox potential. How-ever, the release of co-precipitated heavy metals following the dissolution of Fe-Mn oxyhydroxides could be the mechanism by which reduced condition affected heavy metal solubility considering the decrease of pe as depth increased in tile saturated zone.