The electronic absorption spectra and thermodynamics of axial coordination reaction of 5 (4 glycine butoxyphenyl) 10,15,20 triphenyiporphintozinc with substituted pyridines in CHCl 3 were studied.Coordination numbers ...The electronic absorption spectra and thermodynamics of axial coordination reaction of 5 (4 glycine butoxyphenyl) 10,15,20 triphenyiporphintozinc with substituted pyridines in CHCl 3 were studied.Coordination numbers and equilibrium constants of axial coordination reaction were measured by visible spectra techniques.The changs of standard molar enthalpies and standard molar entropies of reaction were obtained from the plots of ln K vs 1/T.The influence of temperature and axial ligands on the axial reaction were discussed.展开更多
Additive reactions of Ni[(C 4H 9O) 2PS 2] 2 with ethylamine,diethylamine and triethylamine were studied by spectrophotometric methods in ethanol at several tempertures.With ethylamine,the adduct formation of NiL 2...Additive reactions of Ni[(C 4H 9O) 2PS 2] 2 with ethylamine,diethylamine and triethylamine were studied by spectrophotometric methods in ethanol at several tempertures.With ethylamine,the adduct formation of NiL 2·B and NiL 2·B 2 was established.For diethylamine and triethylamine,being of their steric hindrance effect,the formation of NiL 2·B only was concluded.Their additive equilibrium constants(lg β n)and additive molecular number(n) were discussed.Thermodynamic parameters △ r H m and △ r S m were found by the least square method.The additive equilibrium constants in the range 278 0～303 0K were described by empirical equation.展开更多
蚀变分带和成矿机制的准确厘定是建立斑岩成矿模型与找矿预测的关键。本文以新生代金沙江-哀牢山成矿带的玉龙斑岩铜矿为例,通过质量作用定律(LMA)和吉布斯自由能最小化模型(GEM),构建含矿热液与斑岩侵入体的pH-f O 2相图和动态传输模型...蚀变分带和成矿机制的准确厘定是建立斑岩成矿模型与找矿预测的关键。本文以新生代金沙江-哀牢山成矿带的玉龙斑岩铜矿为例,通过质量作用定律(LMA)和吉布斯自由能最小化模型(GEM),构建含矿热液与斑岩侵入体的pH-f O 2相图和动态传输模型,以揭示蚀变分带成因和金属成矿机制。LMA与GEM结果显示初始成矿流体pH值为4.7,logf_(O2)=-23.0(ΔFMQ=+2.7),且溶解Cu含量为1138×10^(-6),Mo为1.2×10^(-6)。研究表明,当该酸性及强氧化性流体流入二长花岗斑岩体时,在温度为450~360℃范围内,代表钾硅酸盐化蚀变的钾长石、黑云母、硬石膏、赤铁矿和磁铁矿的矿物逐渐沉淀,且与钾硅酸盐化蚀变相关流体具有较高pH值(5.0~7.0)和氧逸度(ΔFMQ=+2.9~+3.6)特征;当温度在360~320℃范围时,代表青磐岩化蚀变阶段的典型矿物如绿帘石、铁绿泥石和斜绿泥石等逐渐形成,流体pH值(5.0~6.4)和氧逸度(ΔFMQ=+1.1)均有所下降;当温度进一步从320℃下降到200℃时,流体pH值(5.0~5.7)进一步小幅下降,而氧逸度则(ΔFMQ=+1.7)略有回升,在此期间,绢云母和方解石等开始沉淀并形成典型的绢英岩化蚀变。此外,以HMoO_(4)^(-)和MoO_(4)^(2-)为载体的Mo在狭窄高温区间(450~370℃)内沉淀,而以CuCl(CuCl_(4)^(3-)、CuCl_(2)^(-)、CuCl)为主要载体的Cu则在在中、高温(450~300℃)范围中沉淀。通过利用LMA反演及GEM正演相结合定量化地刻画了玉龙斑岩铜矿水岩反应过程,由此揭示了斑岩矿床蚀变分带是逐渐冷却的单一岩浆热液与斑岩体不断反应的结果,且不同温度窗口对应着钾硅酸盐化(450~360℃)、青磐岩化(360~320℃)和绢英岩化(320~200℃)蚀变矿物的形成,故含矿流体温度的快速下降可能是玉龙铜矿蚀变叠加的重要因素。此外,Cu、Mo络合离子溶解度对温度变化的差异响应,导致了Mo矿化主要发育于靠近斑岩体的高温区域,而Cu则以网脉状-浸染状叠加到Mo矿化之上,并广泛分布于斑岩体周边的高-中温区域。展开更多
文摘The electronic absorption spectra and thermodynamics of axial coordination reaction of 5 (4 glycine butoxyphenyl) 10,15,20 triphenyiporphintozinc with substituted pyridines in CHCl 3 were studied.Coordination numbers and equilibrium constants of axial coordination reaction were measured by visible spectra techniques.The changs of standard molar enthalpies and standard molar entropies of reaction were obtained from the plots of ln K vs 1/T.The influence of temperature and axial ligands on the axial reaction were discussed.
文摘Additive reactions of Ni[(C 4H 9O) 2PS 2] 2 with ethylamine,diethylamine and triethylamine were studied by spectrophotometric methods in ethanol at several tempertures.With ethylamine,the adduct formation of NiL 2·B and NiL 2·B 2 was established.For diethylamine and triethylamine,being of their steric hindrance effect,the formation of NiL 2·B only was concluded.Their additive equilibrium constants(lg β n)and additive molecular number(n) were discussed.Thermodynamic parameters △ r H m and △ r S m were found by the least square method.The additive equilibrium constants in the range 278 0～303 0K were described by empirical equation.
文摘蚀变分带和成矿机制的准确厘定是建立斑岩成矿模型与找矿预测的关键。本文以新生代金沙江-哀牢山成矿带的玉龙斑岩铜矿为例,通过质量作用定律(LMA)和吉布斯自由能最小化模型(GEM),构建含矿热液与斑岩侵入体的pH-f O 2相图和动态传输模型,以揭示蚀变分带成因和金属成矿机制。LMA与GEM结果显示初始成矿流体pH值为4.7,logf_(O2)=-23.0(ΔFMQ=+2.7),且溶解Cu含量为1138×10^(-6),Mo为1.2×10^(-6)。研究表明,当该酸性及强氧化性流体流入二长花岗斑岩体时,在温度为450~360℃范围内,代表钾硅酸盐化蚀变的钾长石、黑云母、硬石膏、赤铁矿和磁铁矿的矿物逐渐沉淀,且与钾硅酸盐化蚀变相关流体具有较高pH值(5.0~7.0)和氧逸度(ΔFMQ=+2.9~+3.6)特征;当温度在360~320℃范围时,代表青磐岩化蚀变阶段的典型矿物如绿帘石、铁绿泥石和斜绿泥石等逐渐形成,流体pH值(5.0~6.4)和氧逸度(ΔFMQ=+1.1)均有所下降;当温度进一步从320℃下降到200℃时,流体pH值(5.0~5.7)进一步小幅下降,而氧逸度则(ΔFMQ=+1.7)略有回升,在此期间,绢云母和方解石等开始沉淀并形成典型的绢英岩化蚀变。此外,以HMoO_(4)^(-)和MoO_(4)^(2-)为载体的Mo在狭窄高温区间(450~370℃)内沉淀,而以CuCl(CuCl_(4)^(3-)、CuCl_(2)^(-)、CuCl)为主要载体的Cu则在在中、高温(450~300℃)范围中沉淀。通过利用LMA反演及GEM正演相结合定量化地刻画了玉龙斑岩铜矿水岩反应过程,由此揭示了斑岩矿床蚀变分带是逐渐冷却的单一岩浆热液与斑岩体不断反应的结果,且不同温度窗口对应着钾硅酸盐化(450~360℃)、青磐岩化(360~320℃)和绢英岩化(320~200℃)蚀变矿物的形成,故含矿流体温度的快速下降可能是玉龙铜矿蚀变叠加的重要因素。此外,Cu、Mo络合离子溶解度对温度变化的差异响应,导致了Mo矿化主要发育于靠近斑岩体的高温区域,而Cu则以网脉状-浸染状叠加到Mo矿化之上,并广泛分布于斑岩体周边的高-中温区域。
