Crystallization of sodium sulfate phases in porous materials: The phase diagram Na2SO4–H2O and the generation of stress

Mechanical disintegration by crystal growth of salts in pores is generally considered as an important mechanism of rock breakdown both on Earth and on Mars. Crystal growth is also a major cause of damage in porous building materials. Sodium sulfate is the most widely used salt in accelerated weathering tests of natural rocks and building materials. This paper provides an updated phase diagram of the Na2SO4–H2O system based on a careful review of the available thermodynamic data of aqueous sodium sulfate and the crystalline phases. The phase diagram includes both the stable phases thenardite, Na2SO4(V), and mirabilite, Na2SO4·10H2O, and, the metastable phases Na2SO4(III) and Na2SO4·7H2O. The phase diagram is used to discuss the crystallization pathways and the crystallization pressures generated by these solids in common laboratory weathering experiments and under field conditions. New crystallization experiments carried out at different temperatures are presented. A dilatometric technique is used to study the mechanical response of sandstone samples in typical wetting–drying experiments as in the standard salt crystallization test. Additional experiments with continuous immersion and evaporation were carried out with the same type of sandstone. Both, the theoretical treatment and the results of the crystallization experiments confirm that the crystallization of mirabilite from highly supersaturated solutions is the most important cause of damage of sodium sulfate in porous materials.

[1]  S. Siegesmund,et al.  Salt and ice crystallisation in porous sandstones , 2007 .

[2]  P. Brimblecombe,et al.  Thermodynamic Properties of Aqueous Aerosols to High Supersaturation: I—Measurements of Water Activity of the System Na+−Cl−−NO− 3−SO2− 4−H2O at ~ 298.15 K , 1997 .

[3]  A. Goudie,et al.  Sodium sulphate weathering and the disintegration of Mohenjo‐Daro, Pakistan , 1977 .

[4]  G. Gülker,et al.  Hydration of MgSO4·H2O and Generation of Stress in Porous Materials , 2008 .

[5]  J. Timmermans The physico-chemical constants of binary systems in concentrated solutions , 1959 .

[6]  Lutz Franke,et al.  Phase changes of salts in porous materials: Crystallization, hydration and deliquescence , 2008 .

[7]  G. Schweiger,et al.  in-situ Raman observation of phase transformation of Na2SO4 during the hydration/dehydration cycles on single levitated microparticle , 1999 .

[8]  H. Hartley,et al.  LXXV.—The spontaneous crystallisation of sodium sulphate solutions , 1908 .

[9]  R. Wilson SOME NEW METHODS FOR THE DETERMINATION OF THE VAPOR PRESSURE OF SALT-HYDRATES. , 1921 .

[10]  George W. Scherer,et al.  Crystallization in pores , 1999 .

[11]  Michael Steiger,et al.  Crystal growth in porous materials—I: The crystallization pressure of large crystals , 2005 .

[12]  G. Schweiger,et al.  単一浮揚微粒子上の水和/脱水サイクルにおけるNa2SO4相変態のin‐situラマン観測 , 1999 .

[13]  H. Silcock Ternary and multicomponent systems of inorganic substances , 1979 .

[14]  H. W. Wellman,et al.  Salt Weathering, a Neglected Geological Erosive Agent in Coastal and Arid Environments , 1965, Nature.

[15]  C. Sperling,et al.  Laboratory simulation of rock weathering by salt crystallization and hydration processes in hot, arid environments , 1985 .

[16]  Robert J. Flatt,et al.  Crystallization damage by sodium sulfate , 2003 .

[17]  J. A. Rard,et al.  Isopiestic Determination of the Osmotic Coefficients of Na2SO4(aq) at 25 and 50°C, and Representation with Ion-Interaction (Pitzer) and Mole Fraction Thermodynamic Models , 2000 .

[18]  Ronan Hébert,et al.  Salt crystallization in pores: quantification and estimation of damage , 2007 .

[19]  J. Selker,et al.  Migration of saline solutions in variably saturated porous media. , 2004, Journal of contaminant hydrology.

[20]  C. Rodriguez-Navarro,et al.  Salt weathering: influence of evaporation rate, supersaturation and crystallization pattern , 1999 .

[21]  Michael Steiger,et al.  Crystallization properties of salt mixtures: comparison of experimental results and model calculations , 1996 .

[22]  K. Linnow,et al.  Investigation of sodium sulfate phase transitions in a porous material using humidity- and temperature-controlled X-ray diffraction. , 2006, Analytical chemistry.

[23]  Eric Doehne,et al.  How does sodium sulfate crystallize? Implications for the decay and testing of building materials , 2000 .

[24]  K. Sing Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity (Recommendations 1984) , 1985 .

[25]  H. Leopold,et al.  THE VAPOR PRESSURE OF THE SATURATED AQUEOUS SOLUTIONS OF CERTAIN SALTS , 1927 .

[26]  A. D. Jensen,et al.  Efflorescence and breakdown of building materials , 1989 .

[27]  Michael Steiger,et al.  Crystal growth in porous materials—II: Influence of crystal size on the crystallization pressure , 2005 .

[28]  D. H. Everett The thermodynamics of frost damage to porous solids , 1961 .

[29]  P. Jacobs,et al.  The role of saline solution properties on porous limestone salt weathering by magnesium and sodium sulfates , 2007 .

[30]  W. Gans Thermodynamic Stability of Sodium Sulfate Heptahydrate , 1978 .

[31]  R. U. Cooke,et al.  Laboratory simulation of salt weathering processes in arid environments , 1979 .

[32]  B. Clark,et al.  The salts of Mars , 1981 .

[33]  Heather Viles,et al.  Salt Weathering Hazard , 1997 .

[34]  W. Giauque,et al.  Relation of crystalline forms I, III, IV, and V of anhydrous sodium sulfate as determined by the third law of thermodynamics , 1972 .

[35]  L. Pel,et al.  Experimental evidence of crystallization pressure inside porous media. , 2005, Physical review letters.

[36]  Robert J. Flatt,et al.  Salt damage in porous materials: how high supersaturations are generated , 2002 .

[37]  I. Tang Thermodynamic and optical properties of mixed‐salt aerosols of atmospheric importance , 1997 .

[38]  A. Goudie,et al.  Laboratory simulation of ‘the wick effect’ in salt weathering of rock , 1986 .

[39]  W. Schumb THE DISSOCIATION PRESSURES OF CERTAIN SALT HYDRATES BY THE GAS-CURRENT SATURATION METHOD , 1923 .

[40]  M. Montoto,et al.  Acoustic emission monitoring to study sodium sulphate crystallization in monumental porous carbonate stones , 1997 .

[41]  E. P. Perman,et al.  The dissociation of sodium sulphate decahydrate , 2022 .

[42]  Andrew Putnis,et al.  Crystallisation of sodium sulfate: supersaturation and metastable phases , 2007 .

[43]  A. Menzies,et al.  The Solubilities of Certain Inorganic Compounds in Ordinary Water and in Deuterium Water. , 1940 .

[44]  Rafael Fort,et al.  Patterns of halite (NaCl) crystallisation in building stone conditioned by laboratory heating regimes , 2007 .

[45]  I. Evans Salt crystallization and rock weathering: a review , 1970 .

[46]  Lutz Franke,et al.  Model for the mechanical stress due to the salt crystallization in porous materials , 2008 .

[47]  D. Benavente,et al.  The influence of petrophysical properties on the salt weathering of porous building rocks , 2007 .

[48]  A. Goudie,et al.  Further experimental investigation of rock weathering by salt and other mechanical processes , 1974 .

[49]  G. P. Baxter,et al.  THE AQUEOUS PRESSURE OF SOME HYDRATED CRYSTALS. OXALIC ACID, STRONTIUM CHLORIDE AND SODIUM SULFATE. , 1920 .

[50]  C. Rodriguez-Navarro Evidence of honeycomb weathering on Mars , 1998 .

[51]  Merle. Randall,et al.  THE FREEZING POINT AND ACTIVITY COEFFICIENT OF AQUEOUS BARIUM NITRATE, SODIUM SULFATE AND SULFURIC ACID , 1927 .

[52]  M. Malin Salt weathering on Mars , 1974 .

[53]  Michael Steiger,et al.  A rapid method for the determination of cation exchange capacities of sandstones: preliminary data , 2002, Geological Society, London, Special Publications.

[54]  H. Stephen,et al.  Solubilities of inorganic and organic compounds , 1963 .

[55]  Wolf-Dieter Grimm,et al.  Bildatlas wichtiger Denkmalgesteine der Bundesrepublik Deutschland , 1990 .

[56]  V. Amirthalingam,et al.  Topotaxic phase change in Na2SO4 , 1977 .

[57]  I. Smalley,et al.  Salt Weathering in Deserts , 1968, Nature.

[58]  A. Trenhaile The Geomorphology of Rock Coasts , 1987 .