Sodium sulfate heptahydrate

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Author: Amelie Stahlbuhk
back to Sulfate


Sodium sulfate heptahydrate
Mineralogical name
Chemical name sodium sulfate heptahydrate
Trivial name
Chemical formula Na2SO4•7H2O
Other forms Na2SO4•10H2O (Mirabilite)
Crystal system
Crystal structure
Deliquescence humidity 20°C 89.1 %
Solubility (g/l) at 20°C 3.143 mol/kg
Density (g/cm³)
Molar volume
Molar weight 268,14 g/mol
Transparency
Cleavage
Crystal habit
Twinning
Phase transition
Chemical behavior
Comments
Crystal Optics
Refractive Indices
Birefringence
Optical Orientation
Pleochroism
Dispersion
Used Literature
[Steiger.etal:2008]Author: Steiger, Michael; Asmussen, Sönke
Journal: Geochimica et Cosmochimica Acta
Number: 17
Pages: 4291-4306
Title: Crystallization of sodium sulfate phases in porous materials: The phase diagram Na2SO4–H2O and the generation of stress
Url: https://doi.org/10.1016/j.gca.2008.05.053
Volume: 72
Year: 2008
Key: sodium sulfate,
Link to Google Scholar


Introduction

Sodium sulfate heptahydrate is a metastable phase of sodium sulfate. Its formation can be observed during the rapid cooling of a solution that is saturated at 40 °C [Gans:1978]Author: Gans, W.
Journal: Zeitschrift für Physikalische Chemie
Number: 1
Pages: 39-46
Title: Thermodynamic stability of sodium sulfate heptahydrate
Url: https://doi.org/10.1524/zpch.1978.111.1.039
Volume: 111
Year: 1978
Link to Google Scholar

Solubility

Figure 1: Solubility of Na2SO4 in water, according to : [Steiger.etal:2008]Author: Steiger, Michael; Asmussen, Sönke
Journal: Geochimica et Cosmochimica Acta
Number: 17
Pages: 4291-4306
Title: Crystallization of sodium sulfate phases in porous materials: The phase diagram Na2SO4–H2O and the generation of stress
Url: https://doi.org/10.1016/j.gca.2008.05.053
Volume: 72
Year: 2008
Key: sodium sulfate,
Link to Google Scholar



The solubility of the heptahydrate at 20 °C is 3.145 mol/kg [Steiger.etal:2008]Author: Steiger, Michael; Asmussen, Sönke
Journal: Geochimica et Cosmochimica Acta
Number: 17
Pages: 4291-4306
Title: Crystallization of sodium sulfate phases in porous materials: The phase diagram Na2SO4–H2O and the generation of stress
Url: https://doi.org/10.1016/j.gca.2008.05.053
Volume: 72
Year: 2008
Key: sodium sulfate,
Link to Google Scholar
. Figure 1 indicates that, eventhough it is a metastable phase, the heptahydrate is more relevant at lower temperatures.

Hygroscopicity


Figure 2:Deliquescence of Na2SO4, according to: [Steiger.etal:2008]Author: Steiger, Michael; Asmussen, Sönke
Journal: Geochimica et Cosmochimica Acta
Number: 17
Pages: 4291-4306
Title: Crystallization of sodium sulfate phases in porous materials: The phase diagram Na2SO4–H2O and the generation of stress
Url: https://doi.org/10.1016/j.gca.2008.05.053
Volume: 72
Year: 2008
Key: sodium sulfate,
Link to Google Scholar


At 20 °C the deliquescence humidity lies at 89.1 %. The values are higher at lower temperatures (table 1).


Table 1: Deliquescnece humidity of sodium sulfate heptahydrate at different round temperatures, according to [Steiger.etal:2008]Author: Steiger, Michael; Asmussen, Sönke
Journal: Geochimica et Cosmochimica Acta
Number: 17
Pages: 4291-4306
Title: Crystallization of sodium sulfate phases in porous materials: The phase diagram Na2SO4–H2O and the generation of stress
Url: https://doi.org/10.1016/j.gca.2008.05.053
Volume: 72
Year: 2008
Key: sodium sulfate,
Link to Google Scholar
0°C 10°C 20°C
96.1%r.h. 93.3%r.h. 89.1%r.h.


The importance of the heptahydrate in the damage process

For more informations see [Saidov:2012]Author: Saidov, Tamerlan Adamovich
Note: https://doi.org/10.6100/IR737583 , ISBN: 978-90-386-3268-1 Salt weathering is widely recognized as one of the most common mechanisms for deterioration of porous materials: monuments, sculptures and civil structures. One of the most damaging salts is sodium sulfate, which can have different crystalline modifications: thenardite (anhydrous), mirabilite (Na2SO4.10H2O), and heptahydrate (Na2SO4.7H2O), which is thermodynamically metastable. Na2SO4.7H2O has a well-defined supersolubility region limited by the so-called heptahydrate supersolubility line. To predict and prevent crystallization damage of porous materials it is necessary to know the salt phase that is responsible for damage as well as its nucleation and growth behavior. The crystallization of sodium sulfate can be induced by increasing the supersaturation either by drying or by cooling of a sample. In this study the supersaturation was measured non-destructively by Nuclear Magnetic Resonance (NMR). First, the crystallization was studied in bulk solutions. For this purpose an NMR setup was combined with time lapse digital microscopy, allowing simultaneous measurement of supersaturation in a droplet and visualization of the crystal growth. Two crystallization mechanisms were tested: diffusion controlled and adsorption controlled. The crystallization of heptahydrate was found to have so-called adsorption-controlled behavior. As a second step towards understanding sodium sulfate crystallization in porous materials, mineral powders were added to sodium sulfate solutions. This allowed studying the transition from in-bulk to in-pore crystallization of sodium sulfate. It was found that mineral powders act as additional nucleation centers, which accelerate the precipitation of crystalline phases from a solution, but do not have an effect on the crystalline phase that is growing. Next, the crystallization of sodium sulfate in porous materials was studied. The internal properties of the materials influence the dynamics of crystallization by providing a surface for nucleation. This is in correspondence with grain-boundary crystallization theory. It was found that the internal properties of porous materials do not influence the crystalline phase that is formed. In all measurements that were performed, the formation of sodium sulfate heptahydrate was observed with a reproducibility of 95%. No spontaneous crystallization of mirabilite directly from a solution was observed. Finally, the crystallization pressure was studied. To this end NMR measurements and optical length measuring techniques were combined. This allowed studying the crystalline phase being formed and the crystallization pressure caused by crystal formation during cooling and drying of the samples. It was found that a crystallization pressure capable to damage common porous materials can be expected from mirabilite. Series of weathering tests showed two ways for mirabilite formation: cooling of sodium sulfate solution to cryohydrates and rewetting of previously formed thenardite. Doctoral degree 30-10-2012; Department of Applied Physics; Supervisors: K. Kopinga and G.W. Scherer; Co-promotor: L. Pel
School: Technische Universiteit Eindhoven
Title: Sodium sulfate heptahydrate in weathering phenomena of porous materials
Type: dissertation
Url: https://pure.tue.nl/ws/portalfiles/portal/3710663/737583.pdf
Year: 2012
Key: sodiumsulfate, heptahydrate
Link to Google Scholar

Weblinks


Literature

[Gans:1978]Gans, W. (1978): Thermodynamic stability of sodium sulfate heptahydrate. Zeitschrift für Physikalische Chemie, 111 (1), 39-46, Url, %doi%Link to Google Scholar
[Saidov:2012]Saidov, Tamerlan Adamovich (2012): Sodium sulfate heptahydrate in weathering phenomena of porous materials. dissertation, Technische Universiteit Eindhoven, Url, %doi%Link to Google Scholar
[Steiger.etal:2008]Steiger, Michael; Asmussen, Sönke (2008): Crystallization of sodium sulfate phases in porous materials: The phase diagram Na2SO4–H2O and the generation of stress. Geochimica et Cosmochimica Acta, 72 (17), 4291-4306, Url, %doi%Link to Google Scholar