Viscosity-temperature relationships in the system Na2Si2O5-Na4Al2O5

The viscosity-temperature relationships of five melts on the join Na₂Si₂O₂-Na₄Al₂O₅ (5, 10, 20, 30 and 40 mole percent Na₄Al₂O₅) have been measured in air, at 1 atm and 1000–1350°C with a concentric cylinder viscometer. All the melts on this join of constant bulk polymerization behave as Newtonian fluids, in the range of shear rates investigated, and the melts exhibit Arrhenian viscosity-temperature relationships.Isothermal viscosities on this join initially decrease and then increase with increasing mole percent Na₄Al₂O₅. The minimum viscosity occurs near 20 mole percent Na₄Al₂O₅ at 1000°C and moves to higher Na₄Al₂O₅ content with increasing temperature.The observation of a viscosity minimum along the join Na₂Si₂-O₅-Na₄Al₂O₅ is not predicted based on earlier viscosity data for the system Na₂O-Al₂O₃-SiO₂ (RlEBLlNG, 1966) or based on calculation methods derived from this and other data (Bottinga and Weill, 1972). This unexpected behavior in melt viscosity-temperature relations emphasizes the need for a more complete data set in simple silicate systems.Previous spectroscopic investigation of melts on the join Na₂2Si₂O₅-Na₄Al₂O₅ offer a structural explanation for the observed viscosity data in terms of a disproportionation reaction involving polyanionic units. Macroscopically, the viscosity data may be qualitatively reconciled with the configurational entropy model for viscous flow (Richet, 1984).     

Raman Micro-Spectroscopic Study of Sulfate Ion in the System Na2SO4 – H2O

This work aims to quantify sulfate ion concentrations in the system Na₂SO₄-H₂O using Raman micro-spectroscopy.Raman spectra of sodium sulfate solutions with known concentrations were collected at ambient temperature（293 K） and in the 500 cm^₁-4000 cm^-1 spectral region.The results indicate that the intensity of the SO₄^2- band increases with increasing concentrations of sulfate ion.A linear correlation was found between the concentration of SO₄^2-（c） and parameter I₁,which represents the ratio of the area of the SO₄^2- band to that of the O-H stretching band of water（A_s/A_w）:I₁=-0.00102+0.01538 c.Furthermore,we deconvoluted the O-H stretching band of water(2800 cm^-1-3800 cm^-1) at 3232 and 3430 cm^-1 into two sub-Gaussian bands,and then defined Raman intensity of the two sub-bands as A_Bi(3232 cm^-1) and A_B2(3430 cm^-1),defined the full width of half maximum（FWHM） of the two sub-bands as W_B1(3232 cm^-1) and W_B2(3430 cm^-1).A linear correlation between the concentration of SO₄^2-（c） and parameter I₂,which represents the ratio of Raman intensity of SO₄^2-（A_s）(in 981 cm^-1) to(A_B1+A_B2),was also established:I₂=-0.0111+0.3653 c.However,no correlations were found between concentration of SO₄^2-（c） and FWHM ratios,which includes the ratio of FWHM of SO₄^2-（W_s） to W_B1 W_B2 and W_B1+B2(the sum of W_B1 and W_B2),suggesting that FWHM is not suitable for quantitative studies of sulfate solutions with Raman spectroscopy.A comparison of Raman spectroscopic studies of mixed Na₂SO₄ and NaCI solutions with a constant SO₄^2- concentration and variable CI^- concentrations suggest that the I\ parameter is affected by CI^-,whereas the I₂ parameter was not.Therefore,even if the solution is not purely Na₂SO₄-H₂O,SO₄^2- concentrations can still be calculated from the Raman spectra if the H₂O band is deconvoluted into two sub-bands,making this method potentially applicable to analysis of natural fluid inclusions.     

过氧化钠超强熔矿能力的新认识

过氧化钠熔融能快速分解许多热稳定性高,化学稳定性好,十分难溶（熔）的矿物、金属、合金、碳化物、氮化物和炉渣等。经长期大量熔矿、测试实验研究认为：过氧化钠超强熔矿能力归因于它在520℃～640℃熔融时,释放出原子氧,将物料中许多元素迅速氧化至最高价态;这些高价离子立即与氧形成络合物;过氧化钠熔融物的强碱性,有利于这些高价离子可熔性络合物的形成和稳定,致使物料的晶体构造、结构彻底破坏,而被完全分解。     

High temperature structural investigation of Na2O·0.5Fe2O3·3SiO2 and Na2O·FeO·3SiO2 melts and glasses

The structure of glasses and melts of Na₂O· 0.5Fe₂O₃·3SiO₂ and Na₂O·FeO·3SiO₂ compositions have been measured using high temperature Raman spectroscopy. For the oxidized sample it has been demonstrated that there is a close structural relationship between melt and glass. No coordination changes of Fe³⁺ with temperature and no new anionic species have been observed in the oxidized melt. The Raman spectra of the reduced sample clearly show a decrease in the degree of polymerization, as determined by the observation of the polarization character of the spectra and the details of the change of the Raman intensities during heating in hydrogen. Mössbauer spectra suggest that Fe³⁺ is tetrahedrally coordinated in the oxidized glass and part of the Fe²⁺ is tetrahedrally coordinated in the reduced glass.     

Internally-Consistent Thermodynamic Data for Minerals in the System Na2O-K2O-CaO-MgO-FeO-Fe2O3-Al2O3-SiO2-TiO2-H2O-CO2

Internally consistent standard state thermodynamic data arepresented for 67 minerals in the system Na₂O-K₂O-CaO-MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-TiO₂-H₂O-CO₂.The method of mathematical programming was used to achieve consistencyof derived properties with phase equilibrium, calorimetric,and volumetric data, utilizing equations that account for thethermodynamic consequences of first and second order phase transitions,and temperature-dependent disorder. Tabulated properties arein good agreement with thermophysical data, as well as beingconsistent with the bulk of phase equilibrium data obtainedin solubility studies, weight change experiments, and reversalsinvolving both single and mixed volatile species. The reliabilityof the thermodynamic data set is documented by extensive comparisons(Figs. 4–45) between computed equilibria and phase equilibriumdata. The high degree of consistency obtained with these diverseexperimental data gives confidence that the refined thermodynamicproperties should allow accurate prediction of phase relationshipsamong stoichiometric minerals in complex chemical systems, andprovide a reasonable basis from which activity models for mineralsmay be derived.     

On the entropy of glaucophane Na2Mg3Al2Si8O22(OH)2

The heat capacity of glaucophane from the Sesia-Lanza region of Italy having the approximate composition (Na_1.93Ca_0.05Fe_0.02) (Mg_2.60Fe_0.41) (Al_1.83Fe_0.15Cr_0.01) (Si_7.92Al_0.08)O₂₂(OH)₂ was measured by adiabatic calorimetry between 4.6 and 359.4 K. After correcting the C _p ⁰ data to values for ideal glaucophane, Na₂Mg₃Al₂Si₈O₂₂(OH)₂ the third-law entropy S ₂₉₈ ⁰ -S ₀ ⁰ was calculated to be 541.2±3.0 J·mol^-1·K^-1. Our value for S ₂₉₈ ⁰ -S ₀ ⁰ is 12.0 J·mol^-1·K^-1 (2.2%) smaller than the value of Likhoydov et al. (1982), 553.2±3.0, is within 6.2 J·mol^-1·K^-1 of the value estimated by Holland (1988), and agrees remarkably well with the value calculated by Gillet et al. (1989) from spectroscopic data, 539 J·mol^-1·K^-1.     

Calculated Phase Relations in High-Pressure Metapelites in the System NKFMASH (Na2O-K2O-FeO-MgO-Al2O3-SiO2-H2O)

Using an internally consistent thermodynamic dataset and updatedmodels of activity–composition relation for solid solutions,petrogenetic grids in the system NKFMASH (Na₂O–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O)and the subsystems NKMASH and NKFASH have been calculated withthe software THERMOCALC 3.1 in the P–T range 5–36kbar and 400–810°C, involving garnet, chloritoid,biotite, carpholite, talc, chlorite, kyanite/sillimanite, staurolite,phengite, paragonite, albite, glaucophane, jadeite, with quartz/coesiteand H₂O in excess. These grids, together with calculated AFMcompatibility diagrams and P–T pseudosections, are shownto be powerful tools for delineating the phase equilibria andP–T conditions of Na-bearing pelitic assemblages for avariety of bulk compositions from high-P terranes around theworld. These calculated equilibria are in good agreement withpetrological studies. Moreover, contours of the calculated phengiteSi isopleths in P–T pseudosections for different bulkcompositions confirm that phengite barometry is highly dependenton mineral assemblage. KEY WORDS: phase relations; HP metapelite; NKFMASH; THERMOCALC; phengite geobarometry     

The System Na2O-Al2O3-Fc2O3-SiO2 at 1 Atmosphere, and the Petrogenesis of Alkaline Rocks

Equilibria involving acmite, albite, nepheline, quartz, anda liquid phase constitute the petrologically important partof the system Na₂O–Al₂O₃–Fe₂O₂–SiO₂, and theunivariant and invariant relations provide useful analogiesfor a wide variety of alkaline igneous rocks. These relationsare dominated by the incongruent melting behaviour of acmite,which does not appear on the liquidus of the join acmite-nepheline-silica;instead, a broad field of hematite is present and acmite crystallizesonly from liquids containing potential sodium silicate. Consequently,the oversaturated and undersaturated eutectics, correspondingto granitic and nepheline syenitic liquids, are rich in sodiumsilicate and distinct from those found in Petrogeny's Residuasystem: the temperatures of the eutectics are 7285C and 7155C, respectively. Survival of peralkaline granite in the aluminouscontinental crust can be explained by the strongly peralkalinecomposition of the oversaturated eutectic. Magma of this typemay be the primitive granite of the non-orogenic zones. Theubiquitous alkali metasomatism around alkaline complexes canalso be interpreted in terms of residual liquids enriched inalkali silicates. Transition from undersaturated to oversaturatedliquids is possible by fractionation of hematite and a new processfor achieving the reverse transition has been found. This dependson the substitution of Fe³ for Al³ in feldspar and suggestsa more important role for syenite in any scheme of petrogenesis. Each of the two eutectics is linked to a corresponding peritecticat which hematite reacts to give acmite. The liquid at the undersaturated,quaternary reaction point is of ijolitic type, providing thefirst intimation that ijolite may represent a low-melting fractionin nature. The system Na₂O–Al₂O₃–Fe₂O₃–SiO₂thus constitutes the peralkaline residua system and on thisbasis a coherent picture of stable continental magmatism canbe constructed. Ijolite is seen as the low-melting fractionfrom a range of peralkaline compositions and from rocks suchas melilite basalt, while the frequently associated carbonatiteis considered to be the volatile-rich, fugitive material fromthe mantle. Such a relationship is consistent with the dualassociation of carbonatite with either ijolite or kimberliteunder different tectonic conditions. The more common syenite,nepheline syenite, and alkaline granite of the non-orogenicregions are regarded as low-melting fractions from basalticmaterials in the deep crust. Most of this activity, involvingmagmas of residual type, could thus be explained in terms ofpartial melting in the deep crust and upper mantle. A possiblemechanism for this would be arching of the rigid continentalcrust, the consequent relief of lithostatic load giving riseto melting, and the concentration of fugitive constituents,in the underlying zones.     

The Effects of Small Amounts of H2O, CO2 and Na2O on the Partial Melting of Spinel Lherzolite in the System CaO-MgO-Al2O3-SiO2 {+/-} H2O {+/-} CO2 {+/-} Na2O at 1{middle dot}1 GPa

The effects of small amounts of H₂O (<4 wt % in the melt)on the multiply saturated partial melting of spinel lherzolitein the system CaO–MgO–Al₂O₃–SiO₂ ±Na₂O ± CO₂ have been determined at 1·1 GPa inthe piston-cylinder apparatus. Electron microprobe analysisand Fourier transform infrared spectroscopy were used to analysethe experimental products. The effects of H₂O are to decreasethe melting temperature by 45°C per wt % H₂O in the melt,to increase the Al₂O₃ of the melts, decrease MgO and CaO, andleave SiO₂ approximately constant, with melts changing fromolivine- to quartz-normative. The effects of CO₂ are insignificantat zero H₂O, but become noticeable as H₂O increases, tendingto counteract the H₂O. The interaction between H₂O and CO₂ causesthe solubility of CO₂ at vapour saturation to increase withincreasing H₂O, for small amounts of H₂O. Neglect of the influenceof CO₂ in some previous studies on the hydrous partial meltingof natural peridotite may explain apparent inconsistencies betweenthe results. The effect of small amounts of H₂O on multiplysaturated melt compositions at 1·1 GPa is similar tothat of K₂O, i.e. increasing H₂O or K₂O leads to quartz-normativecompositions, but increasing Na₂O produces an almost oppositetrend, towards nepheline-normative compositions. KEY WORDS: H₂O; CO₂; FTIR; hydrous partial melting; mantle melting; spinel lherzolite; system CaO–MgO–Al₂O₃–SiO₂ ± H₂O ± CO₂ ± Na₂O     

Calculated Phase Relations in the System Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O with Applications to UHP Eclogites and Whiteschists

Pressure–temperature grids in the system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O and its subsystems have been calculatedin the range 15–45 kbar and 550–900°C, usingan internally consistent thermodynamic dataset and new thermodynamicmodels for amphibole, white mica, and clinopyroxene, with thesoftware THERMOCALC. Minerals considered for the grids includegarnet, omphacite, diopside, jadeite, hornblende, actinolite,glaucophane, zoisite, lawsonite, kyanite, coesite, quartz, talc,muscovite, paragonite, biotite, chlorite, and plagioclase. Compatibilitydiagrams are used to illustrate the phase relationships in thegrids. Coesite-bearing eclogites and a whiteschist from Chinaare used to demonstrate the ability of pseudosections to modelphase relationships in natural ultrahigh-pressure metamorphicrocks. Under water-saturated conditions, chlorite-bearing assemblagesin Mg- and Al-rich eclogites are stable at lower temperaturesthan in Fe-rich eclogites. The relative temperature stabilityof the three amphiboles is hornblende > actinolite > glaucophane(amphibole names used sensu lato). Talc-bearing assemblagesare stable only at low temperature and high pressure in Mg-and Al-rich eclogites. For most eclogite compositions, talccoexists with lawsonite, but not zoisite, in the stability fieldof coesite. Water content contouring of pressure–temperaturepseudosections, along with appropriate geotherms, provides newconstraints concerning dehydration of such rocks in subductingslabs. Chlorite and lawsonite are two important H₂O-carriersin subducting slabs. Depending on bulk composition and pressure–temperaturepath, amphibole may or may not be a major H₂O-carrier to depth.In most cases, dehydration to make ultrahigh-pressure eclogitestakes place gradually, with H₂O content controlled by divariantor higher variance assemblages. Therefore, fluid fluxes in subductionzones are likely to be continuous, with the rate of dehydrationchanging with changing pressure and temperature. Further, eclogitesof different bulk compositions dehydrate differently. Dehydrationof Fe-rich eclogite is nearly complete at relatively shallowdepth, whereas Mg- and Al-rich eclogites dehydrate continuouslydown to greater depth. KEY WORDS: dehydration; eclogites; phase relations; THERMOCALC; UHP metamorphism; whiteschists     

Calculated Phase Relations in the System NCKFMASH (Na2O-CaO-K2O-FeO-MgO-Al2O3-SiO2-H2O) for High-Pressure Metapelites

Petrogenetic grids in the system NCKFMASH (Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O)and the subsystems NCKMASH and NCKFASH calculated with the softwareTHERMOCALC 3.1 are presented for the P–T range 7–30kbar and 450–680°C, for assemblages involving garnet,chloritoid, biotite, carpholite, talc, chlorite, kyanite, staurolite,paragonite, glaucophane, jadeite, omphacite, diopsidic pyroxene,plagioclase, zoisite and lawsonite, with phengite, quartz/coesiteand H₂O in excess. These grids, together with calculated compatibilitydiagrams and P–T and T–X_Ca and P–X_Ca pseudosectionsfor different bulk-rock compositions, show that incorporationof Ca into the NKFMASH system leads to many of the NKFMASH invariantequilibria moving to lower pressure and/or lower temperature,which results, in most cases, in the stability of jadeite andgarnet being enlarged, but in the reduction of stability ofglaucophane, plagioclase and AFM phases. The effect of Ca onthe stability of paragonite is dependent on mineral assemblageat different P–T conditions. The calculated NCKFMASH diagramsare powerful in delineating the phase equilibria and P–Tconditions of natural pelitic assemblages. Moreover, contoursof the calculated phengite Si isopleths in P–T and P–X_Capseudosections confirm that phengite barometry in NCKFMASH isstrongly dependent on mineral assemblage. KEY WORDS: phase relations; metapelites; NCKFMASH; THERMOCALC; phengite geobarometry     

Growth of Emerald Crystals by Evaporation of Na2O—MoO3 Flux

Well-formed crystals of emerald, Be3AI2Si6O18:Cr, were easily grown from an Na2O-MoO3 flux by an isothermal technique. The crystal growth was conducted by heating a mixture of solute and flux at 1 100 ℃ for 24 h. The evaporation loss of flux depended on the amount of Na2O added to MoO3. Emerald crystals of lengths up to 2.1 mm and widths of 1. 4 mm were grown. The crystal sizes were dependent on the evaporation loss of the flux. The obtained crystals were transparent and exhibited the typical emerald-green color. The form of the emerald crystals was a twelve-sided prism bounded by well-developed faces. The aspect ratios were in the region of 1. 4 to 2. 3. The density was (2. 64±0.02) g/cm3. The IR absorption bands were in good agreement with the literature data.     

Thermodynamic Calculation of Solubility of Na2SO4/K2SO4 in Hydrothermal Fluids

Sulfate fluids are common fluids in nature, and their salinity studies can provide important information for the evolution of ore-forming fluids, migration and enrichment of ore-forming elements, and the classification of deposit types. Considerable research has been carried out to investigate the solubility of Na₂SO₄ and K₂SO₄ in hydrothermal fluids, however most of the literature reported experimental data were under saturated vapor pressure or the water supercritical region. A few data have been reported for the low temperature hydrothermal mineralization region. Thermodynamic model is a useful method to study the properties of hydrothermal geofluids, especially for mineral solubility. Pitzer interaction model is one of the most widely used model to calculate the thermodynamic properties of hydrothermal fluids, but few work have ever been carried out to calculate the solubility of sulfate at high temperature and pressure. With Pitzer specific interaction model, using the literature reported density data of Na₂SO₄ and K₂SO₄ solutions at high temperature and pressure, the pressure effect on Pitzer activity coefficient of sulfate and the standard partial molar volume change during sulfate dissolution process were evaluated and related parameters were obtained. The standard partial molar volumes of Na₂SO₄ and K₂SO₄ calculated with these parameters agreed well with those reported in the literature. Combined with the relevant parameters in the literature under saturated vapor pressure, a thermodynamic model for Na₂SO₄ and K₂SO₄ solubility calculation with temperature up to 250 ℃ and pressure up to 40 MPa was developed. The model gave very good agreement with the experimental solubility data. With this model, Na₂SO₄ and K₂SO₄ solubility was calculated at high temperature and pressure. The calculation results showed that pressure had a positive effect on both the average activity coefficient and solubility product of Na₂SO₄ and K₂SO₄, but the solubility of Na₂SO₄ and K₂SO₄ decreased with pressure due to the larger change of the average activity coefficient with pressure. And as the temperature increased, the degree of such reduction became larger. The results herein can provide instructions for the compositional analysis of sulfate fluid inclusions.     

Application of infrared spectroscopy to studies of silicate glass structure: Examples from the melilite glasses and the systems Na2O-SiO2 and Na2O-Al2O3-SiO2

Infrared (IR) and Raman spectroscopic methods are important complementary techniques in structural studies of aluminosilicate glasses. Both techniques are sensitive to small-scale (<15 Å) structural features that amount to units of several SiO₄ tetrahedra. Application of IR spectroscopy has, however, been limited by the more complex nature of the IR spectrum compared with the Raman spectrum, particularly at higher frequencies (1200–800 cm^?1) where strong antisymmetric Si-O and Si-O-Si absorptions predominate in the former. At lower frequencies, IR spectra contain bands that have substantial contributions from ‘cage-like’ motions of cations in their oxygen co-ordination polyhedra. In aluminosilicates these bands can provide information on the structural environment of Al that is not obtainable directly from Raman studies. A middle frequency envelope centred near 700 cm^?1 is indicative of network-substituted AlO₄ polyhedra in glasses with Al/(Al+Si)>0·25 and a band at 520–620cm^?1 is shown to be associated with AlO₆ polyhedra in both crystals and glasses. The IR spectra of melilite and melilite-analogue glasses and crystals show various degrees of band localization that correlate with the extent of Al, Si tetrahedral site ordering. An important conclusion is that differences in Al, Si ordering may lead to very different vibrational spectra in crystals and glasses of otherwise gross chemical similarity.     

The discrete association of water with Na2O and SiO2 in NaAl silicate melts

The solubility of water in several NaAl silicate melts has been determined up to 8 kbars. The results are shown on a (fugacity)^1/2 versus mole percent solubility diagram and data points for any composition can be joined by 2 or more straight lines. It is suggested that each straight line segment represents a different water-solubility mechanism.     

Characteristics of hydrolysis of the complex Na2SnF6 in hydrothermal solutions—An experimental study

Characteristics of hydrolysis of the complex Na₂SnF₆, which is used as the starting material, in hydrothermal solutions have been studied at 200–602°C and 1 kbar. Experimental results show that intense hydrolysis of Na₂SnF₆ occurs at high temperatures and that with the rise of temperature the hydrolysis will become more intense. Under the present experimental conditions the most possible existing form of Sn in the hydrothermal solutions is SnF₃(OH) or Na₂SnF₃(OH). In addition, the hydrolysis constants for Na₂SnF₆ have also been calculated at 200–602°C, and the relationship between Na₂SnF₆ hydrolysis and temperature is discussed.     

Structure and properties of fluorine-bearing aluminosilicate melts: the system Na2O-Al2O3-SiO2-F at 1 atm

The chemical interaction between fluorine and highly polymerized sodium aluminosilicate melts [Al/(Al+Si)= 0.125–0.250 on the join NaAlO₂-SiO₂] has been studied with Raman spectroscopy. Fluorine is dissolved to form F^– ions that are electrically neutralized with Na⁺ or Al³⁺. There is no evidence for association of fluorine with either Si⁴⁺ or Al³⁺ in four-fold coordination and no evidence of fluorine in six-fold coordination with Si⁴⁺ in these melt compositions. Upon solution of fluorine nonbridging oxygens are formed and are a part of structural units with nonbridging oxygen per tetrahedral cations (NBO/T) about 2 and 1. The proportions of these two depolymerized units in the melts increase systematically with increasing F/(F+O) at constant Al/(Al+Si) and with decreasing Al/(Al+Si) at constant F/(F+O). Depolymerization (increasing NBO/T) of silicate melts results from a fraction of aluminum and alkalies (in the present study; Na⁺) reacting to form fluoride complexes. In this process an equivalent amount of Na⁺ (orginally required for Al-³⁺charge-balance) or Al³⁺ (originally required Na⁺ to exist in tetrahedral coordination) become network-modifiers.The structural data have been used to develop a method for calculating the viscosity of fluorine-bearing sodium aluminosilicate melts at 1 atm. Where experimental viscosity data are available, the calculated and measured values are within 5% of each other.A method is also suggested by which the liquidus phase equilibria of fluorine-bearing aluminosilicate melts may be predicted. In accord with published experimental data it is suggested, for example, that — on the basis of the determined solubility mechanism of fluorine in aluminosilicate melts — with increasing fluorine content of feldspar-quartz systems, the liquidus boundaries between aluminosilicate minerals (e.g., feldspars) and quartz shift away from silica.     

Synthesis of tourmaline solid solutions in the system Na2O–MgO–Al2O3–SiO2–B2O3–H2O–HCl and the distribution of Na between tourmaline and fluid at 300 to 700 °C and 200 MPa

Tourmaline has been synthesized hydrothermally at 200 MPa between 300 and 700 °C from oxide mixtures with Mg-Al ratios for the end members dravite NaMg₃Al₆(Si₆O₁₈)(BO₃)₃(OH)₃(OH) and Mg-foitite &ding6F;(Mg₂Al)Al₆ (Si₆O₁₈)(BO₃)₃(OH)₃(OH). Six different Na concentrations were investigated to determine the distribution of Na between tourmaline and fluid in the SiO₂-saturated system Na₂O-MgO-Al₂O₃-SiO₂-B₂O₃-H₂O-HCl. Synthetic tourmaline ranges from X-site vacant (&ding6F;) tourmaline (Mg-foitite) to nearly ideal dravite with Na=0.95 apfu. There are small, but significant, amounts of proton deficiency and negligible tetrahedral Al. Chemical variation is primarily caused by the substitutions Al&ding6F;Mg_-1Na_-1 and minor AlMg_-1H_-1. Varying amounts of Na and &ding6F; determine the Mg/Al ratios. Besides tourmaline and quartz, additional Mg-Al phases are chlorite and, at 700 °C, cordierite. Albite is also present at high Na concentrations in the bulk composition. The c dimension of the tourmaline crystals increases with Na in tourmaline. The amount of Na in the X-site depends strongly on the bulk concentration of Na in the system as well as on the temperature. These factors in turn control the phase assemblage and the composition of the fluid phase. For the assemblage tourmaline + quartz + chlorite/cordierite + fluid, a linear relationship exists between Na concentration in the fluid (quenched after the run) and tourmaline with temperature: T °C [ᆭ °C]=(Na_fluid/Na_tur)앾.878-14.692 (r²=0.96). For the assemblage tourmaline + albite + quartz + fluid, it is: T °C [ᆣ °C]=(Na_fluid/Na_tur)욝.813-6.231 (r²=0.95), where Na_fluid is the concentration of Na⁺ in the final fluid (mol/l) and Na_tur is the number of Na cations in the X-site of tourmaline. The equations are valid in the temperature range of 500-715 °C. Our experiments demonstrate that the occupancy of the X-site in combination with the changing concentrations of Al and Mg can be used to monitor changes in the fluid composition in equilibrium with a growing tourmaline crystal. Currently, this relation can be applied qualitatively to natural tourmaline to explain zoning in Na- and Al/(Al+Mg).