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The Use of Bond Dissociation Energy to Analyze the Geochemical Behavior of Uranium in the Process of Granitic Magmatism
ZHANG BANGTONG ( ~ [ ~ )
(Department of Geology, Nanjing University)
It is estimated that the uranium-oxygen bond dissociation energy(Du4_+0 = 1465.38kJ/mol) is higher than silicon-and aluminium-oxygen bond dissociation energies (Dsi4_+0 = 1264.41 kJ/mol and DAI3_+o= l105.32kJ/mol). During the process of magmatic differentiation with increasing degree of polymerization for silicon-oxygen complex ion, uranium in granitic melts tends to combine with oxygen to form the coordination polyhedron [UOx 2x-'] and to occur in the form of nuclei and crystals of uraninite, as has been demonstrated by the induced fission-track study of quartz syenite from Huangmeijian.
L.Pauling first proposed and described the concept of chemical bond energy in his famous monograph ill. With the advances in spectrometry and mass spectrometry the concept of bond dissociation energy has been established in modern physico-chemistry and found wide application. A handbook of bond dissociation energies was compiled by L.V. Gurvich E21.Y. A. Kosals presented the data on bond dissociation energy for various oxides in granites in his work t31. The author of this paper attempts to explore the geochemical behavior of uranium in the process of granitic magmatism from the point of view of bond dissociation energy. Chemical Properties and Structural Character of Granitic Melts Chemically, granitic melts are composed mainly of the rock-forming elements O, Si, A1, K, Na, Ca, Fe, etc. with minor amounts of other elements. Oxygen is a unique rockforming element which not only is present in maximum amount (47,84wt.% in average granite), but also possesses an electron-shell structure of ls22s22p 4 and easily obtains two electrons to occur in the form of anion. Therefore, metallic elements in the granitic melts are apt to combine with oxygen to form complex anion radicals. Another major element in the granitic melts is silicon, which is estimated at 32.76 wt.% on average. Being highly charged and having a small ionic radius, Si 4§ has a strong preference for oxygen. In the melts, Si 4+ and 0 2-, through sp3-type hybrid orbital, constitute a secure tetrahedron structure by covalent bond. Therefore, silicon-oxygen tetrahedron [SiO4] 4- exists as a basic unit in the structure of granitic melts. Natural granitic magma is a multi-component silicate melt, which contains a portion of other metallic cations (Men§ apart from silicon and aluminium. These cations can also combine with oxygen to form coordination polyhedra [MeOx]2x-n:
.~ [MeOx] 2x-" where Me"+ is the metallic cation. . In recent years bond dissociation energy data for various compounds have been accumulated and compiled into a special handbook. 3 GEOCHEMISTRY 227 Me"+ + xO 2.No. It can be seen from the above calculations that the energies required for dissociation of three U-O bonds are not exactly equal. and [MeOx] 2x-" the coordination polyhedron. The bond dissociation energy of an oxide is defined as the energy required to dissociate the oxide into gaseous Me and O atoms. and the bond energy calculated from thermochemical reaction only represents the average value of bond energy. the strength of combining force of the metallic elements with oxygen can be measured by bond dissociation energy of an oxide.o = 753. The oxide of U 4+ is UO2 and the oxide of U s + is UO 3. but the values of bond dissociation energy can be consulted and calculated more simply than those of bond energy. the difference between the enthalpy of formation of dissociation products and that of formation of oxide: D M e . i. Bond Dissociation Energy and Its Caleulation As stated above.83kJ/mol D u o .76kJ/mol D u . and AHffMeo) is the enthalpy of formation of the metallic oxide (MeO). Duo2-o = 623.o = 711.O = AHf(Me) + AHqo) . For biatomic compounds the values of bond energy and bond dissociation energy are approximately equal. From the handbook of bond dissociation energies[21 the graded bond dissociation energies of uranium oxides are consulted as follows: UO3 = UO2 + O UO 2 = UO + O UO = U + 0 Respective addition gives: DU'+-o = 1465.38Ll/mol and Du6+-o = 2089.e.AHf(MeO) where DMe-o is the bond dissociation energy of a metallic oxide MeO (kJ/mol). Consequently. In the following is an example showing how to calculate the bond dissociation energies of tetravalent and hexavalent uranium oxides.62kJ/mol.21kJ/mol. the geochemical behavior of various metallic elements in the process of magmatism is determined by the competition of the metallic elements with silicon for oxygen. AHf(Me) and AHf(o) are the enthalpies of formation of a metallic element (Me) and oxygen respectively. From the thermodynamic point of view. it is more convenient to discuss the thermodynamical properties of metallic oxides in the light of bond dissociation energy.
52(Zr4+). etc. which can be recognized by their opacity. detailed research in recent years shows that in granites are extensively present micro-grained crystals of uraninite. regular shape (circle). 2432. uraniferous pyrochlore. 1. are 1465. Geochemical Behavior of Uranium during Granitic Magnaatism Silicon-oxygen and aluminium-silicon-oxygen complex ions are the major constitutional units in granitic melts. Ti 4 +. sphene. 5 The DMe-O. brannerite and absite) in Southern Australia.38 (U4+).T -----O M e . euxenite. However. 1356. 1440. we had better compare the bond dissociation energies of oxides of those elements with those of silicon and aluminium oxides. It is considered that uranium in granites is present isomorphously in such accessory minerals as zircon. Y. etc. Ta. distinct boundary and large . U4+. and DAI3§ = 1105. Fe 3 +. U. square crystal form and radioactive polychrom halos surrounding them in thin sections. A13+. brannerite. all being higher than those of silicon and aluminium oxides (Dsi4+_o = 1264. 1369. Ce. and some U deposits (ijolite-syenite. Th and Nb in granitic melts tend to form individual oxide (including complex oxide) minerals. betafite. for example. showt'*l that the variation of bond dissociation energy generally does not exceed 20. Nb. and T is Kelvin temperature.26(Ce4+). polycrase.O . fergusonite. In order to understand the behaviors of uranium and other elements in the process of magmatism. Zr. Th.29ais the bond dissociation energy under standard conditions.T at a given temperature can be calculated with the following formula: DMe--O. respectively.93 kJ/mol and the relative order keeps constant when the temperature rises from 25 ~ to 1300~ Accordingly. the Rossing uranium deposit (alaskite. apatite. the Ross-Adams deposit (alkali-granite. the Charlebois Lake deposit (biotite monzonite. 2 ~ -4- f T ACpdT 298 where DMe-O. These complex ions. uraniferous pyrochlore and rinkolite) in China. Cp is the isostatic heat capacity. It should be emphasized that the radioactive halos around uraninite are different from those around zircon in their dark black color. uraninite and uranothorite) in Alaska of the United States. 1934.84(P s +). fergusonite. P. or dispersed evenly in rock-forming minerals.228 GEOCHEMISTRY Vol. Ca 2 +. thorianite.08(Y 3 +)kJ/mol. such as uraninite.98(Th4+). The bond dissociation energies of oxides of U.41kJ/mol. 1590. the Crocker Well uranium deposit (biotite monzonite.53(TaS+). The calculations of bond dissociation energies of oxides of Si4 +. aluminium and other rock-forming elements to form more stable complex ions (Me02). 1699. uraninite) in Canada. and in a few granite bodies they are even concentrated into magma-type uranium deposits of commercial value.32 kJ/mol).30(NbS+). monazite. uraninite and betafite) in Namibia (South-west Africa). These oxides are mostly present as accessory minerals in granitic rocks. This shows that these elements have a strong tendency to combine with oxygen so that they ca capture part of the oxygen from oxides of silicon. we can analyze the geochemical behavior of various elements in the process of magmatism on the basis of the DMe-0 of oxides under standard conditions without significant errors.
Y. polycrase and pyrochlore. 3 GEOCHEMISTRY 229 radius (several times large as that of other accessory minerals) (Photo 1). mica). and meanwhile free oxygen(O 2-) increases as a result of the decrease in O/Si ratio (R) (Table 1). Ta. It is. Rong Jiashu et al. Zr. xenotime and monazite. Ta. therefore. this process can promote uranium concentration to form uraium oxides (uraninite) in acidic magma. uranium exist~ isomorphously in these accessory minerals (Photos 3--4). Although geologists both in China and abroad discovered micro-grained uraninite in many granites. in the Marnike two-mica granite in France uranium occurring as uraninite comprises about 70 % of the total uranium.2). Zr. allanite. In the process of magmatic evolution. though low uranium content should also be taken into consideration. which is probably the nuclei of supermicro-grained uraninite. the author found that in the microline perthite are scattered some fission-track spots in addition to evenly dispersed tracks which range in diameter from O. . For example. P. From these facts it follows that these densely distributed fission-track spots may indicate the existence of uranium as an independent mineral phase in rock-forming minerals. chain. as the degree of polymerization for silicon-oxygen complex ion increases.or belt-structured silicates as dominating rock-forming minerals. The possible explanation is the lack of 0 2-. etc. These characteristics are quite different from those recognized in zircon and sphene in which uranium is present isomorphously and fission-tracks caused by uranium are homogenously distributed (Photos 3--4). P. n to n gm and increase in number with the content of total uranium (Photo. these elements prefer to form such complex oxides as fergusonite. euxenite. concluded that uraninite can hardly be formed in intermediate or basic rocks with island-. In his induced fission-track investigation of quartz syenite from Huangmeijian. thorianite. Nb. almost no uraninite has been found in intermediate or basic rocks. REE. even in accessory minerals in granodiorite. However. Obviously. Nb. sphene. etc. as well as zircon. Anhui Province.No. the crystal structure of rockforming minerals changes in the order of island -~ ring --* chain --* sheet --* framework. As a result. 3. in the process of crystallization of the granitic magma which has higher conterits of Th. which is characterized by high degree of polymerization for silicon-oxygen polyhedra predominated by framework or sheet structure in the main rock-forming minerals (quartz. Ce. Granite is generally the product of magmatic differentiation-evolution at the late stage. The above facts are sufficient to show that the high uranium-oxygen bond dissociation energy is responsible for the existence of uranium as uraninite or other oxides in granitic rocks. are greater than or approximate to those of uranium oxides. (Beijing Institute of Uranium Geology) pointed out that at least half of the bulk uranium occurs as uraninite in the granite in which the content of uranium exceeds 8 ppm.. feldspar. 2. The bond dissociation energies of oxides of Th.
3 3 4 [Si~O~1]6[Si20512[Si02]2[Al~.~-"--2[Si02]2. [Si20s] 2. a. induced fission-trakcs of uraniun as detected by muscovite detector) 4.45mm. respectively).94 kJ/mol.75 2. which can form glass. Structure type and polymerizing fashion of silicate minerals Structure type Nesosilicate Inosilicate Inosilieate Phyllosilicate Tektosiheate Tektosilicate Complex anion [Si0414[SiO3]~- R = O/Si 4 3 2.22ram. Physico-chemical studies of silicates lSj allow a classification of oxides into three kinds according to the single bond strength: 1) the oxides with the single bond strength > 334.21 k J / m o l are called modificators and their cations are called modifying ions.A.94 k J / m o l are called mediators and their function is intermediate between network-formers and modificators. Anhui (d = 0. sphene.S. Zircon and its induced fission-tracks in biotite-quartz syenite at Huangmeijian. b. plane light. National Bureau of Standards also shows a homogeneous uranium distribution. b.22mm.medium-grained quartz syenite. the synthetic glass with U concentration as high as 500 p p m prepared by U. Induced fission-tracks of uraniumin in microcline perthite of quartz syenite as detected by muscovite detector.21 and 334.5 and 10 ppm. Geological Survey and U.28 k J / m o l . In recent years. Anhui (d = 0.5 2 Number of O-combined cations 0 2 2. Ur uranitite. 5 Table 1. The strength of single bond in u r a n i u m oxides is 366. Such kinds of oxides are called network formers and their cations are called network-forming ions. d = 0.Sic4_~)Os]4- Example t Polymerizing fashion Olivine Pyroxene Hornblende Mica Quartz Feldspar [SiO4]4.Zielinski/6J reported.S. fine-grained quartz syenite) 3. induced fission-tracks of uranium as detected by muscovite detector). and 3) the oxides with the single b o n d strength lying between 251. This feature has been confirmed by geologists of Beijing Institute of Uranium Geology with synthetic uraniferous glass (the contents of uranium are 2. zircon (Zr). a. plane light. Bi biotite. some of which are homogeneously scattered and the rest are distributed like the stars (Hua ngmeijian. . Zr zircon) 2. Anhui. Sphene and its unduced fission-tracks in biotite-quartz syenite at Huangmeijian. 2) the oxides with the single bond strength < 251.+ O2. b.[SiOa] 2. a. the distributional characteristics of uranium in volcanic Photos 1--4: 1. As R. so they are designated to network-formers (or called glass-formers).+ 0 2- 4.+ 02 4[SiOa]2-~-[Si4011] s. Uraninite in biotite from granite at Taoshan.~_.. Jiangxi Province (plane light.45mm. d = 0.+ 02[Si4OH]S-~2[Si2Os] 2.230 GEOCHEMISTRY Vol.
No. 3 GEOCHEMISTHY 231 I O .
so that these elements would prefer to form simple or complex oxides. uranium in volcanic rocks. Zr. Induced fission-track studies revealed that uranium is rather homogeneously concentrated in the glass matrix of volcanic rocks. Leaching experiments on igneous rocks show that the rate of uranium leached from volcanic rocks. Nb. . especially from acid volcanic glass is very low. the leaching rate is about 2% for zircon. Therefore. but can leach out more than 50 percent of total uranium from granitic rocks. etc. which then enters into the network of silicate melts. and its single bond (U-O) strength is 366. Nb. In the process of magmatic differentiationevolution.. 5 rocks have been studied in considerable detail.) and so on. for example. It should be noted that the amount of accessory minerals in volcanic rocks is much less than that in intrusive rocks. It is evident that f'Lxeduranium in granites is present isomorphously in accessory minerals. L.. If the contents of Th. Compositional studies of accessory minerals in intrusive and volcanic rocks from Zhongten. According to Tauson's statistics [71. the bond dissociation energies of which are much greater than or approximate to that of uranium. of Nanjing University show that accessory mineral species in hypabyssal intrusive rocks (monzonitic granite) are almost the same as those in the corresponding volcanic rocks (rhyolite). Conclusion To sum up.TausontTl pointed out that the boiling solution containing 5% soda can extract only 5 . Although the primary uranium in igneous rocks occurs mainly in the three forms mentioned above. A1. the environment of crystallization. Consequently. uranium-oxygen coordination polyhedra would be gradually concentrated into later differentiated granitic melts with increasing degree of Si-O polymerization and 0 2 content. Under rapid cooling conditions the crystal growth of minerals would be restricted. especially in volcanic glass would keep the primary state in the melt and be homogeneously distributed in the matrix of the rocks.1 0 percent of total uranium from volcanic glass. the abundance of other components (Th. etc. uranium in accessory minerals in granitic rocks comprises 40% of that in the whole rocks. and U-leaching rate for accessory minerals is very low. REE. in the melts are relatively high. Fujian Province by Chu Xuejun et al. while uranium occurs isomorphously in these accessory minerals. but also provide important basis for the involvement of the coordination polyhedron [UOx] 2x-n in the network structure of silicate melts. Thereby in the process of crystallization of the granitic melts a portion of uranium would crystallize in the form of oxide(uraninite). REE. depending on such factors as the concentration of uranium.V. especially in the glass matrix. but the content of accessory minerals in the latter rocks is at most one-tenth of that in the former. but in volcanic rocks the fixed uranium comprising 80--90 % of total uranium is-dispersed homogeneously in the matrix. in silicate melts uranium readily combines with 0 2 . etc. This implies that uranium belongs to network-formers. higher than that of oxides of Si. P. usually about one-tenth of that from granite. the bond dissociation energy of U4 + oxide is 1465.to form the coordination polyhedron [UOx] 2x-n.38kJ/mol. < 10% for allanite and about 10% for sphene. their proportions in various types of granite and volcanic rock are different with respect to total uranium.232 GEOCHEMISTRY Vol. The above facts not only indicate a high solubility of uranium in silicate melts.35 kJ/mol.
Bulletin. Geochemical Types and Ore Potential of Granitoids. Geological Soc.. Silicate Physicochemistry. V.Y. <<NAUKA>>.. Moscow. The Nature of the Chemical Bond. Ithaca.V. China Architectural Industry Press. <<NAUKA >>.Han Zehong for his assistance in induced fission-track analysis. izd.  Kosals. 1960.. 105--163(in Russian). <<NAUKA >>. Moscow. of Amer. 3 GEOCHEMISTRY 233 Acknowledgements The author wishes to thank Prof. Press. Geochemistry of Molybdenum in Endogenic Process.A.. 98--100 (in Chinese).Zhang Benren for preparing thin sections and Mr. 1976.. et al. 3--12 (in Russian). R. The Essential Features of the Geochemistry of Rare Elements in Granitic Melts and Solutions.A. Chemical Bond Dissociation Energy. 409--414. L. L.I. izd.  Zhejiang University and Shanghai Chemical Engineering College. N. 185--195 (in Russian). Cornell Univ. Zhang Zhuhuan and Senior Engineer Rong Jiashu for carefully reviewing the manuscript. izd. Y. L.. Moscow.  Reharskii. References  Pauling..  Gurvich. 1980. Novosiberia. <<NAUKA>>. izd.  Zielinski..  Tauson. 89(1978). 1974. 52--72 (in Russian). .V. 1973. Potential Ionization and Electron Affinity. 47--59. 1977. Thanks are due to Mr.No.
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