• Title/Summary/Keyword: Equilibria

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Polymetamorphism of the Odesan Gneiss Complex in the Northeastern area of the Kyonggi Massif, Korea (경기육괴 북동부지역에 분포하는 오대산편마암복합체의 다변성작용)

  • 권용완;김형식;오창환
    • The Journal of the Petrological Society of Korea
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    • v.6 no.3
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    • pp.226-243
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    • 1997
  • The Odesan Gneiss Complex consists of mainly migmatitic gneiss and porphyroblastic gneiss with locally intercated quartzite, amphibolite, marble and leucocratic gneiss. At least two different regional metamorphisms are recognized in the study area. Metamorphic grade of the first metamorphism increases from the K-feldspar-muscovite zone(in which biotite-muscovite-plagioclase-quartz and garnet-biotite-muscovite-K-feldspar-plagioclase-quartz assemblages occur) in the east and southwestern part of the study area to the K-feldspar-garnet zone(in which garnet-biotite-K-feldspar-plagioclase-quartz, biotite-K-feldspar-plagioclase-quartz, garnet-biotite-K-feldspar-plagioclase-sillimanite-spinel-quartz assemblages occur) in the northwestern part. Kyanite is found as inclusions in plagioclase. The second metamorphism is characterised by occurrence of cordierite. The metamorphic grade of 2nd metamorphism decreases radically from the central-western part near Gaeinsan in which cordierite-garnet-sillimanite-biotite-muscovite-quartz, cordierite-garnet-spinel-sillimanite-biotite-muscovite-quartz assemblages representing the garnet-cordierite zone are observed. The garnet-cordierite zone is surrounded by the sillimanite-cordierite zone which shows cordierite-sillimanite-biotite-plagioclase, cordierite-muscovite-biotite-plagioclase and sillimanite-muscovite-biotite-plagioclase assemblages. The peak metamorphic P-T conditions of the first metamorphism calcuted from garnet-biotite-sillimanite-K-feldspar-plagioclase-spinel assemblage are 5.4~7.4 kb and $776-789^{\circ}C$. Real P-T condition of the first metamorphism might be higher than the calcuated P-T condition according to the study based on the phase equilibria. P-T conditions calcuated from the garnet-biotite in plagioclase are 12.5kb and $650^{\circ}C$ which indicate that the P-T path of the first metamorphism had passed a high pressure condition before the peak metamorphic temperature condition. The peak metamorphic P-T conditions of the second metamorphism calcuated from garnet-biotite-cordierite-spinel-quartz assemblage are $680~750^{\circ}C$ at pressures lower than 6 kb. In the Odesan Gneiss Complex, the first metamorphism of medium pressure and high temperature had occurred after the high pressure condition and fast uplift and then the second metamorphism of low pressure condition occurred after sedimentation of the Kuryong Group.

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Characterization of Arsenic Adsorption onto Hematite (적철석(Hematite) 표면의 비소 흡착 특성)

  • Kim, Seong Hee;Lee, Woo Chun;Cho, Hyen Goo;Kim, Soon-Oh
    • Journal of the Mineralogical Society of Korea
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    • v.25 no.4
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    • pp.197-210
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    • 2012
  • Hematite has been known to be the most stable form of various iron (oxyhydr)oxides in the surface environments. In this study, its properties as an adsorbent were examined and also adsorption of arsenic onto hematite was characterized as well. The specific surface area of hematite synthesized in our laboratory appeared to be $31.8g\;m^2/g$ and its point of zero salt effect, (PZSE) determined by potentiometric titration was observed 8.5. These features of hematite may contribute to high capacity of arsenic adsorption. From several adsorption experiments undertaken at the identical solution concentrations over pH 2~12, the adsorption of As(III) (arsenite) was greater than that of As(V) (arsenate). As of pH-dependent adsorption patterns, in addition, arsenite adsorption gradually increased until pH 9.2 and then sharply decreased with pH, whereas adsorption of arsenate was greatest at pH 2.0 and steadily decreased with the increasing pH from 2 to 12. The characteristics of these pH-dependent adsorption patterns might be caused by combined effects of the variation in the chemical speciation of arsenic and the surface charge of hematite. The experimental results on adsorption kinetics show that adsorption of both arsenic species onto hematite approached equilibrium within 20 h. Additionally, the pseudo-second-order model was evaluated to be the best fit for the adsorption kinetics of arsenic onto hematite, regardless of arsenic species, and the rate constant of As(V) adsorption was investigated to be larger than that of As(III).

Spectroscopic Studies on U(VI) Complex with 2,6-Dihydroxybenzoic acid as a Model Ligand of Humic Acid (분광학을 이용한 흄산의 모델 리간드인 2,6-Dihydroxybenzoic acid와 우라늄(VI)의 착물형성 반응에 관한 연구)

  • Cha, Wan-Sik;Cho, Hye-Ryun;Jung, Euo-Chang
    • Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
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    • v.9 no.4
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    • pp.207-217
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    • 2011
  • In this study the complex formation reactions between uranium(VI) and 2,6-dihydroxybenzoate (DHB) as a model ligand of humic acid were investigated by using UV-Vis spectrophotometry and time-resolved laser-induced fluorescence spectroscopy (TRLFS). The analysis of the spectrophotometric data, i.e., absorbance changes at the characteristic charge-transfer bands of the U(VI)-DHB complex, indicates that both 1:1 and 1:2 (U(VI):DHB) complexes occur as a result of dual equilibria and their distribution varies in a pH-dependent manner. The stepwise stability constants determined (log $K_1$ and log $K_2$) are $12.4{\pm}0.1$ and $11.4{\pm}0.1$. Further, the TRLFS study shows that DHB plays a role as a fluorescence quencher of U(VI) species. The presence of both a dynamic and static quenching process was identified for all U(VI) species examined, i.e., ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$. The fluorescence intensity and lifetimes of each species were measured from the time-resolved spectra at various ligand concentrations, and then analyzed based on Stern-Volmer equations. The static quenching constants (log $K_s$) obtained are $4.2{\pm}0.1$, $4.3{\pm}0.1$, and $4.34{\pm}0.08$ for ${UO_2}^{2+}$, $(UO_2)_2{(OH)_2}^{2+}$, and $(UO_2)_3{(OH)_5}^+$, respectively. The results of Stern-Volmer analysis suggest that both mono- and bi-dentate U(VI)-DHB complexes serve as groundstate complexes inducing static quenching.

Metamorphism of the Buncheon and Hongjeas Granitic Gneisses (분천과 홍제사 화강암질 편마암체의 변성작용)

  • 김형수;이종혁
    • The Journal of the Petrological Society of Korea
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    • v.4 no.1
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    • pp.61-87
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    • 1995
  • On the basis of lithology, the Precambrian Hongjesa Granitic Gneiss can be locally zoned into granoblastic granitic gneiss, porphyroblastic granitic gneiss, migmatitic gneiss from its center to the marginal part. There are no distinct differences in mineral assemblages by lithologic zoning, but it partly shows the change of mineral assemblage in the adjacent with migmatitic gneiss, thus mineral assemblage can be subdivided into Zone I and Zone II. In terms of mineral compositions, the characteristics of Zone I are coexisting K-feldspar+muscovite+sillimanite. The characteristics of Zone II are (1) breakdown of muscovite, (2) coexisting garnetScordierite, (3) coexisting garnet+cordierite + orthoamphibole. The Buncheon Granitic Gneiss is mainly composed of augen gneiss. In the adjacent area with Honjesa Granitic Gneisses, Buncheon Granitic Gneiss has the mineral assemblage of sillimanite+biotite+K-feldspar+(kyanite). Kyanite occurs as relict grains in the Buncheon and Hongjesa Granitic Gneissess. Kyanite shows anhedral to subhedral form and coexists with sillimanite in only one of these samples. Garnet from a migmatitic gneiss (Zone 11) has relatively high $X_{Fe}$ value in core and rim. Garnet from a porphyroblastic granitic gneiss(Zone I) has relatively homogemeous core but compositionally-zoned rim. Biotites show various colour from greenish-brown, brown to reddish brown at maximum adsorption. Also, the Ti, and Mg content in biotites increases from Zone I to Zone II. The plagioclases shows the chemical composition of $Ab_{84}An_{16}$ -$Ab_{70}An_{30}$ (oligoclase) in Zone I and $Ab_{70}An_{30}$ -$Ab_{50}An_{50}$(andesine) in Zone 11. These variations indicate that the gneisses in the study area experienced a upperamphibolite facies. The presence of kyanite as relict grains indicates that the metamorphic rocks in this area exprienced a high-temperature/medium-pressure type metamorphism, followed by high-temperaturellow-pressure metamorphism. Metamorphic P-T conditions for each gneiss estimated from various geothermobarometers and phase equilibria are 698-$729^{\circ}C$/6.3-11.3 kbar in augen gneiss, 621-$667^{\circ}C$/1.0-5.4 kbar in migmatitic gneiss, and 602-$624^{\circ}C$/1.9-3.4 kbar in porphyroblastic granitic gneiss. These data suggest that the study area was subjected to a clockwise P-T path with isothermal decompression (dP/dT=about 60 bar/$^{\circ}C$).

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Mineralogy and Genetic Environments of the Seongdo Pb-Zn deposit, Goesan (괴산 성도 연-아연 광상의 산출광물과 생성환경)

  • Ahn, Seongyeol;Shin, Dongbok
    • Economic and Environmental Geology
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    • v.50 no.5
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    • pp.325-340
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    • 2017
  • The Seongdo Pb-Zn deposit, located in the northwestern part of the Ogcheon Metamorphic Belt, consists of skarn ore replacing limestone within the Hwajeonri Formation of Ogcheon Group and hydrothermal vein ore filling the fracture of host rock. Skarn minerals comprise mostly hedenbergitic pyroxene, garnet displaying oscillatory zonal texture composed of grossular and andradite, and a small amount of wollastonite, tremolite, and epidote, indicating reducing condition of formation. Ore minerals of skarn ore include sphalerite and galena with a small amount of pyrite, pyrrhotite, and chalcopyrite. In hydrothermal vein ore, arsenopyrite, sphalerite, chalcopyrite, and pyrite occur with a small amount of galena, native Bi, and stannite. Chemical compositions of sphalerite vary from 17.4 mole% FeS in average for dark grey sphalerite, 3.6 mole% for reddish brown sphalerite in skarn ore, and to 10.3 mole% FeS in hydrothermal vein ore. In comparison with representative metallic deposits in South Korea on the FeS-MnS-CdS diagram, skarn and hydrothermal vein ore plot close to the field of Pb-Zn deposits and Au-Ag deposits, respectively. Arsenic contents of arsenopyrite in hydrothermal vein ore decrease from 31.93~33.00 at.% in early stage to 29.58~30.21 at.% in middle stage, and their corresponding mineralizing temperature and sulfur fugacity are $441{\sim}490^{\circ}C$, $10^{-6}{\sim}10^{-4.5}atm$. and $330{\sim}364^{\circ}C$, <$10^{-8}atm$. respectively. Phase equilibrium temperatures calculated from Fe and Zn contents for coexisting sphalerite and stannite in hydrothermal vein are $236{\sim}254^{\circ}C$. Sulfur isotope compositions are 5.4~7.2‰ for skarn ore and 5.4~8.4‰ for hydrothermal vein ore, being similar or slightly higher to magmatic sulfur, suggesting that ore sulfur was mostly of magmatic origin with partial derivation from host rocks. However, much higher sulfur isotope equilibrium temperatures of $549^{\circ}C$$487^{\circ}C$, respectively for skarn ore and hydrothermal ore, than those estimated from phase equilibria imply that isotopic equilibrium has not been fully established.

Modeling on the Sorption Kinetics of Lead and Cadmium onto Natural Sediments (퇴적물에서의 납과 카드뮴의 흡착 동력학 모델링)

  • Kwak, Mun-Yong;Ko, Seok-Oh;Park, Jae-Woo;Jeong, Yeon-Gu;Shin, Won-Sik
    • Korean Journal of Ecology and Environment
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    • v.39 no.4 s.118
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    • pp.450-461
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    • 2006
  • In this study, sorption kinetics of lead (Pb) and cadmium (Cd) onto coastal sediments were investigated at pH 5.5 using laboratory batch adsorbers. Four different models: one-site mass transfer model (OSMTM), pseudo-first-order kinetic model (PFOKM) ,pseudo-second-order kinetic model (PSOKM) and two compartment first-order kinetic model (TCFOKM) were used to analyze the sorption kinetics. As expected from the number of model parameters involved, the three-parameter TCFOKM was better than the two-parameter OSMTM, PFOKM and PSOKM in describing sorption kinetics of Pb and Cd onto sediments. Most sorption of Pb and Cd was rapidly completed within the first three hours, followed by slow sorption in the subsequent period of sorption. All models predicted that the sorbed amount at the apparent sorption ($q_{e,s}$) equilibria increased as the CEC and surface area of the sediments increased, regardless of initial spiking concentration ($C_0$) and heavy metal and the sediment type. The sorption rate constant ($k_s,\;hr^{-1}$) in OSMTM also increased as the CEC and BET surface area increased. The rate constant of pseudo-first-order sorption ($k_{p1,s},\;hr^{-1}$) in PFOKM were not correlated with sediment characteristics. The results of PSOKM analysis showed that the rate constant of pseudo-second-order sorption ($k_{p2,s},\;g\;mmol^{-1}\;hr^{-1}$) and the initial sorption rate ($v_{o,s},\;mg\;g^{-1}\;hr^{-1}$) were not correlated with sediment characteristics. The fast sorption fraction ($f_{1,s}$) in TCFOKM increased as CEC and BET surface increased regardless of initial aqueous phase concentrations. The sorption rate constant of fast fraction ($k_{1,s}=10^{0.1}-10^{1.0}\;hr^{-1}$) was much greater than that of slow sorption fraction ($k_{2,s}=10^{-2}-10^{-4}\;hr^{-1}$) respectively.

Phase Behavior of Poly(methylmethacrylate) (PMMA) in Varions Solvents at High Pressure (고압상태의 다양한 용매 내에서 Poly(methylmethacrylate) (PMMA)의 상거동)

  • Kim, Je-Il;Yoo, Ki-Pung;Lim, Jong-Sung
    • Clean Technology
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    • v.13 no.1 s.36
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    • pp.28-33
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    • 2007
  • We measured cloud points of Poly(methylmethacrylate) (PMMA) in various solvents using the high-pressure variable volume view cell apparatus. The solvents used for dissolving PMMA were chlorodifluoromethane (HCFC-22), dimethylether (DME), 1,1,1-trifluoroethane (HFC-143a), 1,1-difluoroethane (HFC-152a) and 1,1,1,2-tetrafluoroethane (HFC-134a), and the effect of $CO_2$ concentration on the phase behavior of $PMMA+HCFC-22+CO_2$ system and $PMMA+DME+CO_2$ system was observed. PMMA was dissolved well in HCFC-22 from about 340 K, 5MPa and in DME from about 300 K, 28MPa. However, PMMA was not dissolved at all up to 423.15 K, 160MPa in the other fluorine compound such as HFC-l43a, HFC-152a and HFC-134a. PMMA+HCFC-22, $PMMA+HCFC-22+CO_2$ and PMMA+DME systems exhibit the lower critical solution temperature (LCST) behavior, however, $PMMA+DME+CO_2$ system exhibits the upper critical solution temperature (UCST) behavior. In the $CO_2$ mixture, the cloud point pressure of PMMA was increased dramatically proportional to the amount of $CO_2$ added, and from this result, it was known that $CO_2$ could be used as an antisolvent for fabricating PMMA nano-particles. And the cloud point of PMMA could be controlled by changing the concentration of $CO_2$.

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Thermodynamic Properties for the Chemical Reactions of [Cu(dl-trans-[14]-diene)]$^{2+}$ with S$_2O_3^{2-},\;SCN^-,\;I^-\;and\;NO_2^-$ ([Cu(dl-trans-[14]-diene)]$^{2+}$ 착이온과 음이온 (S$_2O_3^{2-},\;SCN^-,\;I^-$ 및 NO$_2^-$)간의 화학반응에 대한 열역학적 성질 (${\Delta}G;\;{\Delta}H;\;{\Delta}V$))

  • Yu Chul Park;Jong Chul Byun
    • Journal of the Korean Chemical Society
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    • v.29 no.3
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    • pp.239-246
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    • 1985
  • The equilibria of chemical reaction between [Cu(dl-trans-[14]-diene)]$^{2+}$ and L$^{n-}$(S$_2$O$_3^{2-}$, SCN$^-$, I$^-$, NO$_2^-$) ions were studied by the spectrophotometric method in the range of 15 to 35$^{\circ}C$ and 1 to 1500bar. The equilibrium constants(K) for L$^{n-}$ = S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ and NO$_2^-$ ions at 25$^{\circ}C$ and 1500bar were 3.0, 1.9, 0.6 and 0.5, respectively. The values of K decreased with increasing pressure and temperature. From the temperature effect on equlibrium constant, the thermodynamic parameters(${\Delta}G^{\circ}$, ${\Delta}H^{\circ}$, ${\Delta}S^{\circ}$) of reaction were evaluated and the reactions of [Cu(dl-trans-[14]-diene)]2+ ion with S$_2$O$_3^{2-}$, SCN$^-$ and I$^-$ except NO$_2^-$ ion were exothermic. The volume changes of reaction(${\Delta}$V) had positive values for all the used anions. The values of ${\Delta}$V in cm$^3$/mole for S$_2$O$_3^{2-}$ ion at 1,500, 1,000 and 1,500bar were 26, 22, 19 and 16, and those for S$_2$O$_3^{2-}$, SCN$^-$, I$^-$ and NO$_2^-$ ions at atmospheric pressure 26, 30, 64 and 45, respectively. Bonding character between Cu(Ⅱ)-complex ion and L$^{n-}$ was discussed by comparing both the equlibrium constants experimentally determined and those calculated according to Fuoss's ion-pair equation in case of S$_2$O$_3^{2-}$ ion.

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Geochemistry of Geothermal Waters in Korea: Environmental Isotope and Hydrochemical Characteristics I. Bugok Area (한반도 지열수의 지화학적 연구: 환경동위원소 및 수문화학적 특성 I. 부곡 지역)

  • Yun, Seong-Taek;Koh, Yong-Kwon;Kim, Chun-Soo;So, Chil-Sup
    • Economic and Environmental Geology
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    • v.31 no.3
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    • pp.185-199
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    • 1998
  • Hydrogeochemical and environmental isotope studies were undertaken for various kinds of water samples collected in 1995-1996 from the Bugok geothermal area. Physicochemical data indicate the occurrence of three distinct groups of natural water: Group I ($Na-S0_4$ type water with high temperatures up to $77^{\circ}C$, occurring from the central part of the geothermal area), Group II (warm $Na-HCO_{3}-SO_{4}$ type water, occurring from peripheral sites), Group III ($Ca-HCO_3$ type water, occurring as surface waters and/or shallow cold groundwaters). The Group I waters are further divided into two SUbtypes: Subgroup Ia and Subgroup lb. The general order of increasing degrees of hydrogeochemical evolution (due to the degrees of water-rock interaction) is: Group III$\rightarrow$Group II$\rightarrow$Group I. The Group II and III waters show smaller degrees of interaction with rocks (largely calcite and Na-plagioclase), whereas the Group I waters record the stronger interaction with plagioclase, K-feldspar, mica, chlorite and pyrite. The concentration and sulfur isotope composition of dissolved sulfate appear as a key parameter to understand the origin and evolution of geothermal waters. The sulfate was derived not only from oxidation of sedimentary pyrites in surrounding rocks (especially for the Subgroup Ib waters) but also from magmatic hydrothermal pyrites occurring in restricted fracture channels which extend down to a deep geothermal reservoir (typically for the Subgroup Ia waters). It is shown that the applicability of alkaliion geothermometer calculations for these waters is hampered by several processes (especially the mixing with Mg-rich near-surface waters) that modify the chemical composition. However, the multi-component mineral/water equilibria calculation and available fluid inclusion data indicate that geothermal waters of the Bugok area reach temperatures around $125^{\circ}C$ at deep geothermal reservoir (possibly a cooling pluton). Environmental isotope data (oxygen-18, deuterium and tritium) indicate the origin of all groups of waters from diverse meteoric waters. The Subgroup Ia waters are typically lower in O-H isotope values and tritium content, indicating their derivation from distinct meteoric waters. Combined with tritium isotope data, the Subgroup Ia waters likely represent the older (at least 45 years old) meteoric waters circuated down to the deep geothermal reservoir and record the lesser degrees of mixing with near-surface waters. We propose a model for the genesis and evolution of sulfate-rich geothermal waters.

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Phase Equilibria of the System Pd-Sb-Te and Its Geological Implications (팔라듐-안티몬-테루르 계(系)의 상평형(相平衡)과 지질학적(地質學的) 의의(意義))

  • Kim, Won-Sa;Chao, George Y.
    • Economic and Environmental Geology
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    • v.26 no.3
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    • pp.327-335
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    • 1993
  • Phase relations in the system Pd-Sb-Te were investigated at $1000^{\circ}$, $800^{\circ}$, and $600^{\circ}C$, using the sealed-capsule technique; the quenched products were studied by reflected light microscopy, X-ray diffraction, and electron microprobe analysis. At $1000^{\circ}C$, the solid phases Pd, $Pd_{20}Sb_7$, $Pd_8Sb_3$, $Pd_{31}Sb_{12}$, and $Pd_5Sb_2$ are stable with a liquid phase that occupies most of the isothermal diagram. Additional solid phases at $800^{\circ}C$ are $Pd_5Sb_3$, PdSb, $Pd_8Te_3$, $Pd_7Te_3$, and a continuous $Pd_{20}Te_7-Pd_{20}Sb_7$ solid solution becomes stable. At $600^{\circ}$, $PdSb_2$, $Pd_{17}Te_4$, $Pd_9Te_4$, PdTe, $PdTe_2$, $Sb_2Te_3$, and Sb and continuous PdSb-PdTe and $PdTe-PdTe_2$ solid solutions are stable. All the solid phases exhibit solid solution, mainly by substitution between Sb and Te to an extent that varies with temperature of formation. The maximum substitution (at.%) of Te for Sb in the Pd-Sb phases is: 44.3 in $Pd_8Sb_3$, 52.0 in $Pd_{31}Sb_{12}$, 46.2 in $Pd_5Sb_2$ at $800^{\circ}C$; 15.3 in $Pd_5Sb_3$, 68.3 in $PdSb_2$ at $600^{\circ}C$. The maximum substitution (at.%) of Sb for Te in the Pd-Te phases is 34.5 in $Pd_5Sb_3$ at $800^{\circ}C$, and 41.6 in $Pd_7Te_3$, 5.2 in $Pd_{17}T_4$, 12.4 in $Pd_9Te_4$, and 19.1 in $PdTe_2$ at $600^{\circ}C$. Physical properties and X-ray data of the synthetic $Pd_9Te_4$, PdTe, $PdTe_2$, $Pd_8Sb_3$, PdSb, and $Sb_2Te_3$ correspond very well with those of telluropalladinite, kotulskite, merenskyite, mertieite II, sudburyite, and tellurantimony, respectively. Because X-ray powder diffraction data consistently reveal a 310 peak ($2.035{\AA}$), the $PdSb_2$ phase is most probably of cubic structure with space group $P2_13$. The X-ray powder pattern of a phase with PdSbTe composition, synthesized at $600^{\circ}C$, compares well with that of testibipalladite. Therefore, testibiopalladite may be a member of the $PdSb_2-Pd(Sb_{0.32}Te_{0.68})$ solid solution series which is cubic and $P2_13$ in symmetry. Thus the ideal fonnula for testibiopalladite, presently PdSbTe, must be revised to PdTe(Sb, Te). Borovskite($pd_3SbTe_4$) has not been found in the synthetic system in the temperature range $1000^{\circ}-600^{\circ}C$.

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