239 lines
8.9 KiB
XML
239 lines
8.9 KiB
XML
<?xml version="1.0"?>
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<!--
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NaCl modeling Based on the Silvester&Pitzer 1977 treatment:
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(L. F. Silvester, K. S. Pitzer, "Thermodynamics of Electrolytes:
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8. High-Temperature Properties, including Enthalpy and Heat
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Capacity, with application to sodium chloride",
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J. Phys. Chem., 81, 19 1822 - 1828 (1977)
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This modification reworks the Na+ standard state Shomate
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polynomial, so that the resulting DeltaG0 for the NaCl(s) -> Na+ + Cl-
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reaction agrees closely with Silvester and Pitzer. The main
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effect that this has is to change the predicted Na+ heat capacity
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at low temperatures.
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-->
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<ctml>
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<phase id="NaCl_electrolyte" dim="3">
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<speciesArray datasrc="#species_waterSolution">
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H2O(L) Cl- H+ Na+ OH-
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</speciesArray>
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<state>
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<temperature units="K"> 298.15 </temperature>
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<pressure units="Pa"> 101325.0 </pressure>
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<soluteMolalities>
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Na+:6.0954
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Cl-:6.0954
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H+:2.1628E-9
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OH-:1.3977E-6
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</soluteMolalities>
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</state>
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<thermo model="HMW">
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<standardConc model="solvent_volume" />
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<activityCoefficients model="Pitzer" TempModel="complex1">
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<!-- Pitzer Coefficients
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These coefficients are from Pitzer's main
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paper, in his book.
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-->
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<A_Debye model="water" />
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<ionicRadius default="3.042843" units="Angstroms">
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</ionicRadius>
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<binarySaltParameters cation="Na+" anion="Cl-">
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<beta0> 0.0765, 0.008946, -3.3158E-6,
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-777.03, -4.4706
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</beta0>
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<beta1> 0.2664, 6.1608E-5, 1.0715E-6 , 0.0, 0.0</beta1>
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<beta2> 0.0 , 0.0, 0.0, 0.0, 0.0 </beta2>
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<Cphi> 0.00127, -4.655E-5, 0.0,
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33.317, 0.09421
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</Cphi>
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<Alpha1> 2.0 </Alpha1>
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</binarySaltParameters>
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<binarySaltParameters cation="H+" anion="Cl-">
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<beta0> 0.1775, 0.0, 0.0, 0.0, 0.0</beta0>
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<beta1> 0.2945, 0.0, 0.0, 0.0, 0.0 </beta1>
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<beta2> 0.0, 0.0, 0.0, 0.0, 0.0 </beta2>
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<Cphi> 0.0008, 0.0, 0.0, 0.0, 0.0 </Cphi>
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<Alpha1> 2.0 </Alpha1>
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</binarySaltParameters>
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<binarySaltParameters cation="Na+" anion="OH-">
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<beta0> 0.0864, 0.0, 0.0, 0.0, 0.0 </beta0>
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<beta1> 0.253, 0.0, 0.0, 0.0, 0.0 </beta1>
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<beta2> 0.0, 0.0, 0.0, 0.0, 0.0 </beta2>
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<Cphi> 0.0044, 0.0, 0.0, 0.0, 0.0 </Cphi>
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<Alpha1> 2.0 </Alpha1>
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</binarySaltParameters>
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<thetaAnion anion1="Cl-" anion2="OH-">
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<theta> -0.05 </theta>
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</thetaAnion>
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<psiCommonCation cation="Na+" anion1="Cl-" anion2="OH-">
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<theta> -0.05 </theta>
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<Psi> -0.006 </Psi>
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</psiCommonCation>
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<thetaCation cation1="Na+" cation2="H+">
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<theta> 0.036 </theta>
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</thetaCation>
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<psiCommonAnion anion="Cl-" cation1="Na+" cation2="H+">
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<theta> 0.036 </theta>
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<Psi> -0.004 </Psi>
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</psiCommonAnion>
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</activityCoefficients>
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<solvent> H2O(L) </solvent>
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</thermo>
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<elementArray datasrc="elements.xml"> O H C E Fe Si N Na Cl </elementArray>
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<kinetics model="none" >
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</kinetics>
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</phase>
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<speciesData id="species_waterSolution">
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<species name="H2O(L)">
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<!-- H2O(L) liquid standard state -> pure H2O
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The origin of the NASA polynomial is a bit murky. It does
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fit the vapor pressure curve at 298K adequately.
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-->
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<atomArray>H:2 O:1 </atomArray>
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<thermo>
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<NASA Tmax="600.0" Tmin="273.14999999999998" P0="100000.0">
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<floatArray name="coeffs" size="7">
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7.255750050E+01, -6.624454020E-01, 2.561987460E-03, -4.365919230E-06,
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2.781789810E-09, -4.188654990E+04, -2.882801370E+02
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</floatArray>
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</NASA>
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</thermo>
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<standardState model="waterIAPWS">
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<!--
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Molar volume in m3 kmol-1.
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(this is from Pitzer, Peiper, and Busey. However,
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the result can be easily derived from ~ 1gm/cm**3)
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<molarVolume> 0.018068 </molarVolume>
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-->
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</standardState>
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</species>
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<species name="Na+">
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<!-- Na+ rework. Differences in the delta_G0 reaction
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for salt formation were dumped into this polynomial.
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-->
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<atomArray> Na:1 E:-1 </atomArray>
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<charge> +1 </charge>
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<thermo>
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<Shomate Pref="1 bar" Tmax=" 593.15" Tmin=" 293.15">
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<floatArray size="7">
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-57993.47558 , 305112.6040 , -592222.1591 ,
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401977.9827 , 804.4195980 , 10625.24901 ,
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-133796.2298
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</floatArray>
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</Shomate>
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</thermo>
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<standardState model="constant_incompressible">
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<!-- Na+ (aq) molar volume
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Molar volume in m3 kmol-1.
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(this is from Pitzer, Peiper, and Busey. We divide
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NaCl (aq) value by 2 to get this)
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-->
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<molarVolume> 0.00834 </molarVolume>
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</standardState>
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</species>
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<species name="Cl-">
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<!-- Cl- (aq) standard state based on the unity molality convention
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The Shomate polynomial was created from the SUPCRT92
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J. Phys Chem Ref article, and the CODATA recommended
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values. DelHf(298.15) = -167.08 kJ/gmol
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S(298.15) = 56.60 J/gmolK
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There was a slight discrepancy between those two, which was
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resolved in favor of CODATA.
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Notes: the order of the polynomials can be decreased by
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dropping terms from the complete Shomate poly.
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-->
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<atomArray> Cl:1 E:1 </atomArray>
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<charge> -1 </charge>
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<standardState model="constant_incompressible">
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<!-- Cl- (aq) molar volume
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Molar volume in m3 kmol-1.
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(this is from Pitzer, Peiper, and Busey. We divide
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NaCl (aq) value by 2 to get this)
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-->
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<molarVolume> 0.00834 </molarVolume>
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</standardState>
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<thermo>
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<Shomate Pref="1 atm" Tmax=" 623.15" Tmin=" 298.00">
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<floatArray size="7">
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56696.2042 , -297835.978 , 581426.549 ,
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-401759.991 , -804.301136 , -10873.8257 ,
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130650.697
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</floatArray>
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</Shomate>
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</thermo>
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</species>
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<species name="H+">
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<!-- H+ (aq) standard state based on the unity molality convention
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The H+ standard state is set to zeroes by convention. This
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includes it's contribution to the molar volume of solution.
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-->
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<atomArray> H:1 E:-1 </atomArray>
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<charge> +1 </charge>
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<standardState model="constant_incompressible">
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<molarVolume> 0.0 </molarVolume>
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</standardState>
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<thermo>
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<Mu0 Pref="100000.0" Tmax="625.15." Tmin="273.15">
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<H298 units="cal/mol"> 0.0 </H298>
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<numPoints> 3 </numPoints>
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<floatArray size="3" title="Mu0Values" units="Dimensionless">
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0.0 , 0.0, 0.0
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</floatArray>
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<floatArray size="3" title="Mu0Temperatures">
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273.15, 298.15 , 623.15
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</floatArray>
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</Mu0>
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</thermo>
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</species>
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<species name="OH-">
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<!-- OH- (aq) standard state based on the unity molality convention
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The Shomate polynomial was created with data from the SUPCRT92
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J. Phys Chem Ref article, and from the CODATA recommended
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values. DelHf(298.15) = -230.015 kJ/gmol
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S(298.15) = -10.90 J/gmolK
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There was a slight discrepancy between those two, which was
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resolved in favor of CODATA.
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Notes: the order of the polynomials can be decreased by
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dropping terms from the complete Shomate poly.
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-->
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<atomArray> O:1 H:1 E:1 </atomArray>
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<charge> -1 </charge>
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<standardState model="constant_incompressible">
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<!-- OH- (aq) molar volume
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This value is currently made up.
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-->
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<molarVolume> 0.00834 </molarVolume>
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</standardState>
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<thermo>
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<Shomate Pref="1 atm" Tmax=" 623.15" Tmin=" 298.00">
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<floatArray size="7">
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44674.99961 , -234943.0414 , 460522.8260 ,
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-320695.1836 , -638.5044716 , -8683.955813 ,
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102874.2667
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</floatArray>
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</Shomate>
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</thermo>
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</species>
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</speciesData>
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</ctml>
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