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Think Simulation! Adventures in Electrolytes
OLI Simulation Conference 2012
Advances in Thermodynamics
October 16, 2012
Scope • Review of Mixed-Solvent Electrolyte model
• Application highlights for various chemistries
• Actinide solution chemistry: microcosm of MSE
• CO2 – H2O – salt systems: key chemistry in nature
• Improved temperature and pressure dependence of parameters: density and heat capacity of salt solutions
• Si chemistry: importance of speciation
• Salts in nonaqueous solvents: battery electrolytes
• Additional thermophysical properties
• Interfacial tension
• Improvement of thermal conductivity model
• Guidelines for selecting the MSE and AQ thermodynamic models
• Plans for future development
MSE thermo thermo Standard-
state: HKF
(direct)
GEX: MSE no limit on
concentration
Solid phases: thermochemical
properties
Surface
tension
Interfacial
tension 2nd liquid phase:
MSE (ionic)
Electrical conductivity
Viscosity
Thermal
conductivity
Self -
diffusivity
Interfacial phenomena: ion exchange, surface
complexation, molecular adsorption
Mixed-Solvent Electrolyte
Framework
RT
G
RT
G
RT
G
RT
G exII
exLC
exLR
ex
LR Long-range electrostatic interactions
LC Local composition term for neutral molecule interactions
II Ionic interaction term for specific ion-ion and ion-molecule interactions
Mixed-Solvent Electrolyte Model: Selected New Chemistries in 2010-2012
• Inorganic systems
• CO2 – salt – water chemistry
• Alkaline earth metal solution chemistry (with common anions): Be, Sr, Ba
• Transition metal solution chemistry: V, Mo, Fe, Ni, Cu(I), Zn, Hg
• Post-transition metal solution chemistry: Ga
• Metalloid solution chemistry: Si
• Actinide solution chemistry: U, Pu, Am
• Selected sulfamates, cyanides, perchlorates
• Densities up to high temperatures and pressures
• Improved heat capacities
Mixed-Solvent Electrolyte Model: Selected New Chemistries in 2010-2012
• Organic and organic/inorganic systems
• Main alkanolamine – CO2 – H2S systems
• Selected carbohydrates
• Caprolactam process chemistry
• Phenol – H2SO4 – NaOH chemistry
• Hydrocarbon – salt – water systems
• LiPF6 and LiBF4 in nonaqueous organic carbonate solvents
• Selected nitriles and heterocyclic nitrogen-containing compounds in water
• Selected fuel oxygenate components
• Selected oxalates
Modeling actinide (U, Pu, Am) chemistry: Microcosm of MSE
• Solubility of oxides / hydroxides as a function of pH
• Accuracy controlled by the standard-state properties of species (dilute solutions)
Hydrolyzed forms
Complexes (with carbonates, peroxides, etc.)
• Behavior in HNO3 solutions
• Very high solubilities
• Accuracy controlled by MSE interaction parameters
• Double salt formation (with Mo, Cs, etc.)
• Multiple redox states
Pu solubility as a function of pH
t = 25oC
1.0E-11
1.0E-10
1.0E-09
1.0E-08
1.0E-07
1.0E-06
1.0E-05
1.0E-04
1.0E-03
1.0E-02
1.0E-01
1.0E+00
0 2 4 6 8 10 12 14 16 18
pH
m-P
u
Pu(III): Pu(OH)3PPT
Pu(IV): Pu(OH)4PPT
Pu(V): PuO2OHPPT
Pu(VI): PuO2(OH)2.H2O
Pu(V)
Pu(III) Pu(VI)
Pu(IV)
• Amphoteric character: importance of hydrolyzed species
• Key oxidation states: III, IV, V, and VI
• Pu(III) and Pu(V) are unstable due to disproportionation (V) and oxidation (III)
Uranium (VI) Solubility in UO3 + HNO3 + H2O system
UO3.H2O
59C
50C
40C
30C
25C
UO3
HNO3H2O
UO3.H2O
UO2(NO3)2.6H2O
UO2(NO3)2.3H2O
UO2(NO3)2.2H2O
• Very concentrated nitrate solutions
• Multiple hydrates of UO2(NO3)2
• Hydration number decreases with rising HNO3 content
CO2 /carbonate chemistry Importance of both H2O-rich and CO2-rich
phases
• CO2 – H2O binary • Major improvement for the CO2-rich phase
• CO2 – H2O – salt systems: Water-rich phases • Extensively data are available
• Comprehensive parameterization for CO2 – HCO3 – CO3 – Cl – Na – K – Mg – Ca – Sr – Ba systems
• CO2 – H2O – salt systems: CO2-rich phases • Not studied in the literature
• Crucial for CO2 sequestration and mineral carbonation
Mineral transformations are controlled by both water content and high CO2 partial pressure
• Joint project with PNNL: New water content data
• MSE can predict composition of CO2-rich phases based on parameters obtained from H2O-rich phases
9
Water content in CO2 – rich
phase
• Transition from VLE to LLE behavior as pressure increases
• MSE methodology:
• MSE liquid phase model + vapor EOS in VLE region
• MSE liquid phase model for both H2O- and CO2-rich phases in LLE region
• Transition region is important in CO2 sequestration
15 – 40 °C
50 – 75 °C
Effect of salt content in the H2O-rich phase on the water content in the
CO2 – rich phase
• Pure prediction: parameters were derived from data for H2O-rich phases only
• Water in CO2 is needed for mineral transformations
• A change in water content of CO2 phase changes the reactivity of minerals Dashed lines: Minimum water content that is
necessary for transformation of forsterite, Mg2SiO4, into nesquehonite MgCO3∙3H2O
Densities up to high T and P
• Temperature and pressure dependence of ion interaction parameters has been made more flexible
• This is necessitated by the inherent P and T dependence of standard-state properties, especially at higher temperatures
• Densities can be represented now up to 4000 atm
800
850
900
950
1000
1050
1100
1150
1200
1250
1300
0 1000 2000 3000 4000
Den
sity
,g/l
P / atm
20
C
1.9 m0.9 m 0.17 m
0.017 m
800
850
900
950
1000
1050
1100
1150
1200
1250
1300
0 1000 2000 3000 4000
Den
sity
,g/l
P / atm
200
C
5.7 m3.75 m
1.9 m0.9 m 0.17 m
0.017 m
Si chemistry: Importance of
speciation
• A model for SiO2 in the liquid phase was developed previously
• Solubility in the liquid phase was excellent up to 350 C and 2000 atm
• Solubility in the gas phase was very bad
0
100
200
300
400
500
600
700
800
0 50 100 150 200 250 300 350
pp
m S
iO2
t/C
saturation pressure
Beckwith and Reeve 1969
Crerar and Anderson 1971
Fournier 1960
Hemley et al. 1980
Kennedy 1950
Kitahara 1960
Morey et al. 1962
Rimstidt 1997
Siever 1962
van Lier et al. 1960
Prediction
0
200
400
600
800
1000
1200
1400
0 50 100 150 200 250 300 350
pp
m S
iO2
t/C
p=1000 atm
Hemley et al. 1980
Kennedy 1950
Morey et al. 1962
Ragnasrdottir and Walther 1983
Walther and Orville 1983
Wang et al. 2004 (+/- 200 atm)
Weill and Fyfe 1964
Prediction
Hydrated silica (H4SiO4) in the gas phase
• By introducing a hydrated form, H4SiO4, solubility of SiO2 in the gas phase can be reproduced without changing the SiO2 properties in the liquid phase
1E-14
1E-13
1E-12
1E-11
1E-10
1E-09
1E-08
0.0000001
0.000001
0.00001
0.0001
0 50 100 150 200 250 300 350
y S
iO2
t/C
Martynova et al. 1975
Plyasunov 2012, silica
MSE silica
Plyasunov 2012, quartz
MSE quartz
SiO2 in the gas and liquid
phases
• MSE reproduces the solubility of SiO2 in both the gas and liquid phases up to 400 C and 2000 atm
• It agrees with the solubility transition from vapor-like to liquid-like region
1.E-09
1.E-08
1.E-07
1.E-06
1.E-05
1.E-04
1.E-03
1.E-02
10 100 1000
x S
iO2
p H2O [atm]
Martynova et al. 1975, t=262.72C
Heitmann 1964, t=265C
MSE, t=262.72C, silica
MSE, t=262.72C, quartz
Morey and Hesselgesser 1951, t=400C silica
Heitmann 1964, t=400C
MSE, t=400C, silica
Morey and Hesselgesser 1951, t=400C quartz
MSE, t=400C, quartz
V-L transition at 262.72 C
Near-critical transition at 400 C
Nonaqueous systems: LiPF6 and LiBF4 in organic carbonates
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
-40 -30 -20 -10 0 10 20 30 40 50t / C
x L
iBF
4
DMC
LiBF4.2DMC
LiBF4.0.5DMC
DMC - calculated
LiBF4.2DMC - calculated
LiBF4.0.5DMC - calculated
• Components of lithium batteries
• Polar solvents: mixed organic carbonates
• Lithium salts are highly soluble and conductive in organic carbonates
• Phase behavior includes the formation of salt – carbonate adducts
LiBF4 + dimethyl carbonate
Modeling interfacial tension
Interfacial tension of a
partially miscible mixture
in the absence of electrolyte:
Mixing rule in terms of phase
compositions and interfacial
area (related to volume)
contribution
of electrolytes
eelectrolytms
MSE thermodynamic model
for speciation calculations
i
inti
21
ii 1RT
Aexpxx
31A
32inti
inti NvA
0
10
20
30
40
50
60
70
80
0.0 0.2 0.4 0.6 0.8 1.0
X-PHENOL
T/C
LLE
phenol + water
0.0
0.2
0.4
0.6
0.8
1.0
1.2
0 20 40 60 80
t, C
, m
N.m
-1
0.0
1.0
2.0
3.0
4.0
5.0
6.0
7.0
8.0
0 20 40 60 80
t, C
, m
N.m
-1
Phenol + water: IFT decreases with increased mutual solubility
0
10
20
30
40
50
60
70
80
0.001 0.01 0.1 1
xtriethylaminet,
C
TEA + water: IFT increases with decreased mutual solubility
Interfacial tension vs. mutual solubility
-20
0
20
40
60
80
100
120
0.01 0.1 1
xC4H9OH
t, C
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1.8
2.0
-20 0 20 40 60 80 100 120
t, C
,
mN
.m-1
n-butanol + water: IFT shows a maximum as solubility exhibits a min.
Structure of the model
The Gibbs equation
Relates interfacial tension to activities and surface excess of species
Adsorption isotherm
Defines interfacial concentrations (surface excess)
Introduces interactions of species at the interface
MSE model
Provides activity coefficients and speciation
Effects of electrolytes on interfacial tension – eelectrolyt
Effect of electrolytes on interfacial tension:
Hydrocarbons + water + NaCl
30.0
35.0
40.0
45.0
50.0
55.0
60.0
65.0
0.0 0.5 1.0 1.5 2.0 2.5
{mNaCl, mol.kgH2O-1
}0.5
, m
N.m
-1
o-xylene (1997LHDS)
benzene (1916HH)
n-dodecane (1976AS)
n-octane (1997DV&1996CYG)
n-hexane (1939E)
Organic + H2O + NaCl (20~25oC)
increases with salt concentration for most systems The change in can be attributed
to the combined effects of
Solubility: Salting-out solubility
Ionic interactions at the interface can cause an increase or decrease in
Mutual solubilities from MSE predict trends of interfacial tension with salt concentration
Revision of thermal conductivity model: Pressure dependence
total wt% = 15
0.52
0.54
0.56
0.58
0.60
0.62
0.64
0.66
0.68
0.70
0.72
280 330 380 430 480 530 580
T/K
l, W
∙m-1
∙K-1
5 MPa
10 MPa
20 MPa
30 MPa
40 MPa
50 MPa
wt% KCl = wt% CaCl2
(wt% NaCl) / (wt% CaCl2) = 3
b. • Introducing pressure dependence of parameters
• Effect of pressure is comparable to the effect of electrolyte concentration
• Important for seawater applications
T and P dependence for a NaCl - KCl - CaCl2 - H2O mixture at constant concentration
MSE thermo thermo Standard-
state: HKF
(direct)
GEX: MSE no limit on
concentration
Solid phases: thermochemical
properties
AQ thermo Standard-state: HKF (via fitting
equations)
GEX: Bromley-Zemaitis
I < 30m; xorg < 0.3
Solid phases: equilibrium
constants (Kfits)
Surface
tension
Interfacial tension
2nd liquid phase:
MSE (ionic)
2nd liquid phase:
SRK (non-ionic)
Electrical conductivity
Electrical
conductivity
Viscosity Viscosity
Self -
diffusivity
Thermal
conductivity
Self -
diffusivity
Interfacial phenomena: ion exchange, surface
complexation, molecular adsorption
MSE vs. AQ frameworks
Databank statistics • MSE model
• Continued growth of the MSEPUB databank:
1709 species in October 2010
1825 species in October 2011 (version 8.3.6)
1900 species in September 2012 (version 9.0.1)
1933 species in October 2012 (version 9.0.2)
• Corrosion (CRMSE) databank
323 species
• Geochemical (GEMSE) databank
130 species
• Aqueous model
• Small increase of the number of species
5403 species in PUBLIC
373 species in CORROSIO
139 species in GEOCHEM
MSE vs. AQ: Practical aspects
• Why is the MSE databank still much smaller than AQ?
• A much larger number of organic solutes in AQ, valid in relatively dilute solutions
• A large number of aqueous complexes
Chelants are not available in MSE
• A limited number of species with some anions in MSE (Br, I)
• A limited number of species with some less-common elements in MSE (e.g., As, Sb, Bi, Se, Rb, Cs, Th, Np, Pt group)
MSE vs. AQ: Practical aspects
• Why is MSEPUB currently growing by only ~ 6-7% per year?
• All parameters are introduced only based on critical evaluation and regression of primary experimental data (VLE, SLE, LLE, speciation, Hex, etc.)
• Thermochemical parameters are never introduced straight from the literature
• Standard-state properties are never introduced without consideration of solution nonideality
• Detailed validation spreadsheets are maintained
MSE vs. AQ: Selecting the model
• Current default in the software: AQ
• Larger database
• The only model available for corrosion kinetics
• The only model available in ScaleChem Standard (transition to Studio ScaleChem is under way)
• MSE parameters for hydrocarbons are being revised
• However, numerous systems can be modeled only with MSE or can be modeled much better
MSE vs. AQ: Selecting the model
• Examples of chemistries that can be handled only by MSE
• Oil and gas chemistry in the presence of glycols and methanol
• Sublimation equilibria
• Refinery overhead chemistry
• Ionic liquids
• CO2 – rich phases
• Electrolytes in nonaqueous solvents
• Electrolytes in two liquid phases (e.g., I-S chemistry)
• Extraction systems with electrolytes
• Concentrated nitrate chemistry
• Acid-base chemistry in mixed solvents
• Urea chemistry
• Caprolactam chemistry
MSE vs. AQ: Selecting the model
• Examples of chemistries that can be modeled much better by MSE than by AQ
• Power plant chemistry (transition metals, B, Li, Si, etc.)
• Hydrometallurgical systems
• Corrosion product chemistry
• Nuclear waste chemistry
• Carbohydrate chemistry
• In general, multicomponent salt systems
• What is needed to change the default to MSE?
• Revision of hydrocarbon parameters
• Improvement of properties of common gases, including the effect of electrolytes
Plans for Future Development
• Development of MSE thermodynamic parameters
• Client-directed targeted chemistry studies
• Broad-based advancements in parameterization
Hydrocarbon – water – electrolyte mixtures
Gases in the presence of electrolytes
Organic sulfur species
Hydrometallurgical chemistry (with University of Toronto)
Many others
• Additional thermophysical properties
• Finalize the model for interfacial tension
• Develop a model for mutual diffusivity
Foundation for improved mass-transfer separations
Chemistry Coverage in the MSEPUB Databank (1)
• Binary and principal ternary systems composed of the following primary ions and their hydrolyzed forms
• Cations: Na+, K+, Mg2+, Ca2+, Al3+, NH4+
• Anions: Cl-, F-, NO3-, CO3
2-, SO42-, PO4
3-, OH-
• Multicomponent Na salts
• Na+ - F- - NO3- - NO2
- - CO32- - SO4
2- - OH- - PO43-
• Li chemistry
• Li+ - K+ - Mg2+ - Ca2+ - Cl-
• Li+ - BO2- - H+, F-, CO3
2-
• Cs chemistry
• Cs+ - NO3-
• Ba chemistry
• Ba2+ - Cl- - CO32- - SO4
2- - OH- - BO2- - NO3
- - H+ - Na+ - K+ - Mg2+ - Ca2+ - Sr2+
• Sr chemistry
• Sr2+ - Cl- - CO32- - SO4
2- - NO3- - H+ - Na+ - K+ - Mg2+ - Ca2+ - Ba2+
• Borate chemistry
• H+ - Li+ - Na+ - Mg2+ - Ca2+ - BO2- - OH-
• H+ - Li+ - Na+ - BO2- - HCOO- - CH3COO- - Cl- - OH-
In red: Additions and revisions since Oct. 2011
• Aqueous acids, associated acid oxides and acid-containing mixtures
• H2SO4 – SO3
• HNO3 – N2O5
• HNO2
• H3PO4 – H4P2O7 – H5P3O10 – P2O5
• H3PO2
• H3PO3
• HF
• HCl
• HBr
• HI
• H3BO3
• NH2SO3H
• HClO4
Chemistry Coverage in the MSEPUB Databank (2)
•HFSO3 – HF – H2SO4
•HI – I2 – H2SO4
•HNO3 – H2SO4 – SO3
•HCl – H2SO4
•H3PO4 with calcium phosphates
•H+ – Na+ – Cl- – NO3-
•H+ – Na+ – Cl- – F-
•H+ – Na+ – PO43- - OH-
•H+ – NH3 – NO3- – SO4
2-
•H+ – NH3 – Cl-
•H+ – Na – Ca – Cl – SO4
•H+ – Mg – Ca – Cl – SO4
•H+ - NH2SO3- - NH4
+ - SO42-
• Sulfide and H2S chemistry (other than transition metals)
• NH4HS + H2S + NH3 • H2S – H+ – Na+ - Cl-
• Na2S – NaHS – H2S
• Inorganic gases in aqueous systems • CO2 - NH3 - H2S
• CO2 - Li+ - Cl- - CO32-
• CO2 - Na+ - Cl- - CO32-
• CO2 - K+ - Cl- - CO3
2-
• CO2 - Mg+ - Cl- - CO32-
• CO2 - Ca+ - Cl- - CO32-
• SO2 - H2SO4
• N2
• O2 • H2 – H+ – Na+ - Cl-
• NO
Chemistry Coverage in the MSEPUB Databank (3)
• Beryllium chemistry • BeII – H+ - OH- - Na+, K+, CO3
2-, S2- • Silicate/aluminosilicate chemistry
• SiIV – H+ - OH- - Na+
• Na+ - SiO32- - OH-
• SiIV – F- - HF – ClO4-
• Aluminosilicates
Cancrinite, hydrosodalite, zeolite A, sodium aluminosilicate gel
• Gallium chemistry
• Ga3+ - H+ - OH- - SO42- - Na+ - K+
• Perchlorate chemistry
• Na+ - Mg2+ - ClO4- - CO2
• Hydrogen peroxide chemistry
• H2O2 – H2O – H – Na – OH – SO4 – NO3
Chemistry Coverage in the MSEPUB Databank (4)
• Fe chemistry • FeII – H+ – OH- – Cl- - Br- - SO4
2- - NO3- - S2- - Ac- - NH3 - NH4
+ - Na+
• FeII – CrIII – H+ - OH-
• FeII - Na+ - PO43-
• FeII - CO32- - Cl- - ClO4
- - Na+
• FeIII – H+ - OH- – Cl- - SO42- - NO3
- - Br-
• FeIII – Ca2+ - H+ – Cl- - SO42-
• FeIII - Na+ - PO43-
• Co chemistry • CoII – H+ - SO4
2-
• Ni chemistry • NiII – H+ - OH- – Cl- - SO4
2- - NO3- - PO4
3- - S2- - NH3 - NH4+ - Na+ - morpholine
• NiII – CrIII – H+ - OH-
• NiII – TiIV – H+ - OH-
• NiII – FeII – H+ - OH- – BO2-
• NiII – Ca2+ - SO42-
Chemistry Coverage in the MSEPUB Databank (5)
• Cr chemistry • CrIII – H+ - OH- – Cl- - SO4
2- - NO3-
• CrVI – H+ - OH- – NO3-
• Mo chemistry • MoIII – H+ - Cl- - OH- - H2
• MoIV – H+ - Cl- - OH- - H2
• MoVI – H+ – OH- – Na+ – NH4+ – Cl- - SO4
2- - NO3- - S2- - H2O2
• MoVI - Ni2+- Fe3+
• W chemistry • WVI – H+ - OH- – Na+ – Cl-, NO3
-
• WIV – H+ - OH-
• Cu chemistry • CuII – H+ – OH- - Cl- - SO4
2- - NO3- – H2S - S2- - CO2 – CO3
- – NH3 - Na+ - morpholine – Et2NH
• CuI – H+ – OH- - SO32-
• CuI – H2S - S2-
• CuII – CuI – FeII – FeIII – H+ - OH- - S2-
Chemistry Coverage in the MSEPUB Databank (6)
• Sn chemistry • SnII – H+ – OH- – CH3SO3
-
• SnIV – H+ – OH- – Cl-
• Zn chemistry • ZnII – H+ - OH- – Cl- - SO4
2- - NO3-
• ZnII – H+ - Li+ - Cl-
• ZnII – H+ - Ca2+ - SO42-
• ZnII - FeIII
• Ti chemistry • TiIV – H+ – OH- – Ba2+ – Cl- - OH- - BuO- – Na+
• Zr chemistry • ZrIV – H+ - OH- - Li+ - Na+ - K+ - Cl- - NO3
- - H2O2
• ZrIV – MoVI – NO3-
• Pb chemistry • PbII – H+ - OH- – Na+ – Cl- – SO4
2- - S2- - H2S - CO32- - ClO4
- – K+ – Si4+
• PbII – TiIV, ZrIV– H+ - OH-
• PbIV – H+ - OH-
Chemistry Coverage in the MSEPUB Databank (7)
• V chemistry • VIII - H+
- OH- - S2-
• VIV - H+ - OH- - SO4
2-
• VV - H+ - OH- - Cl- - SO4
2- - NO3- - Na+ - NH4
+ - Fe3+
• Hg chemistry • HgII – H+ – OH- – Cl-
• HgI - NO3-
• Mn chemistry • MnII – H+ - Ca2+ - SO4
2-
• Ag, Tl chemistry • AgI – TlI – NO3
-
Chemistry Coverage in the MSEPUB Databank (8)
• U chemistry • UIV – H+ – OH- – H2O2 – Na+, K+, Mg2+, Cl-, ClO4
-, CO32-, NO3
-, SO42-
• UVI - MoVI - NO3-
• Pu chemistry • PuIII – H+ – OH-
• PuIV – H+ – OH- - H2O2 - Na+, Cs+, Cl-, ClO4-, NO3
-
• PuIV - MoVI - NH4+ - Cl-
• PuV – H+ – OH- - Na+
• PuVI - H+ – OH- - NO3-
• Am chemistry • AmIII – H+ – OH- – Na+ – Ca2+ – Cl- – ClO4
- – CO32- - CO2
• AmIV – H+ – OH-
• AmIII – S2-
• Nd chemistry • NdIII – H+ – OH-, Cl-
• NdIII – S2-
Chemistry Coverage in the MSEPUB Databank (9)
• Multicomponent metal systems: • CaSO4 – ZnSO4 – MgSO4 – MnSO4 – Na2SO4 – (NH4)2SO4 – H2SO4
• CaSO4 – ZnSO4 – Fe2(SO4)3 – ZnSO4 – H2SO4
• CaSO4 – NiSO4 – Fe2(SO4)3 – LiCl – H2SO4
• Cyanide chemistry
• HCN – CN- – Na+ – NH4+ - NH3
• Iodide chemistry
• I- - K+
Chemistry Coverage in the MSEPUB Databank (10)
• Urea chemistry
• CO2 – NH3 – H2O – NH4CO2NH2 – NH2CONH2
• (H2NCO)2NH (biuret) – H2O
• HNCO - NH4NCO – H2O
• (HNCO)3 (cyanuric acid) – H2O
• Miscellaneous inorganic systems in water • NH2OH – H2SO4 – NH3
• Na2S2O3
• Na+ - BH4- – OH-
• Na+ - SO32- - SO2
- OH-
• Br2 – H2O
• PF5 - H2O
• T2O – HTO
• Most elements from the periodic table in their elemental form
• Base ions and hydrolyzed forms for the majority of elements
Chemistry Coverage in the MSEPUB Databank (11)
• Organic acids/salts in H2O/alcohols • Formic
H+ - Li+ - Na+ - Formate - OH-
Formic acid – MeOH – EtOH - benzene
• Acetic
H+ - Li+ - Na+ - K+ - Ca2+ - Ba2+ - Acetate - OH-
Acetic acid – MeOH – EtOH – CO2
• Propionic
H+ - K+ - Ca2+ - propionate
• Butyric
H+ - K+ - Ca2+ - butyrate
• Heptanoic
H+ - K+ - Ca2+ - heptanoate
• Oxalic
H+ - oxalate – Cl- - SO42-, NO3
-, MeOH, EtOH, 1-PrOH
Na+ - H+ - oxalate
•Citric
•H+ - Na+ - Citrate – OH-
•Malic
•Glycolic
•Adipic
H+ - Na+ - Adipate
Adipic acid – MeOH, EtOH
•Nicotinic
H+ - Na+ - Nicotinate
Nicotinic acid - EtOH
•Terephthalic
H+ - Na+ - Terephthalate
Terephthalic acid – MeOH, EtOH
•Isophthalic
Isophthalic acid - EtOH
•Trimellitic
Trimellitic acid - EtOH
Chemistry Coverage in the MSEPUB Databank (12)
• Organic acids/salts in water and alcohols
• Acrylic
Acrylic – acetic acid
Acrylic – butanol
Complexes with Cu, Ni, Fe, Cr
• Methanesulfonic
• p-Toluenesulfonic
• 2-Phosphonobutane-1,2,4-tricarboxylic (PBTC)
Chemistry Coverage in the MSEPUB Databank (13)
• Hydrocarbon systems
• Hydrocarbon + H2O systems Straight chain alkanes: C1 through C30
Isomeric alkanes: isobutane, isopentane, neopentane
Alkenes: ethene, propene, 1-butene, 2-butene, 2-methylpropene
Alkynes: acetylene
Aromatics: benzene, toluene, o-, m-, p-xylenes, ethylbenzene, cumene, naphthalene, anthracene, phenantrene
Cycloalkanes: cyclohexane, decalin
• Hydrocarbon + salt parameters H3O
+, NH4+, Li+, Na+, K+, Mg2+, Ca2+, Cl-, OH-, HCO3
-, CO32- NO3
-, SO42-
generalized interaction parameters between hydrocarbons (and
pseudocomponents) and other ions
• Hydrocarbon + H2S systems
Chemistry Coverage in the MSEPUB Databank (14)
• Amines (including mixtures with H2O and hydrocarbons)
• Alkylamines:
Primary: methylamine, ethylamine, propylamine, n-butylamine, cyclohexylamine, ethylenediamine, 3-methoxypropylamine
Secondary: dimethylamine, diethylamine, sec-butylamine
Tertiary: trimethylamine, triethylamine, tri-n-octylamine
Mixed amines: methylamine – dimethylamine – trimethylamine
• Alkanolamines
methyldiethanolamine, monoethanolamine, diethanoloamine, 2-dimethylaminoethanol, dimethylisopropanolamine, diglycolamine
Monoethanolamine, diethanolamine, diglycolamine, methyldiethanolamine - CO2 - H2S
• Heterocyclic amines
N-methylpyrrolidone, morpholine, N-methylmorpholine, N-ethylmorpholine, 2,6-dimethylmorpholine
Morpholine - CO2
• Generalized interactions with hydrocarbons
Chemistry Coverage in the MSEPUB Databank (15)
• Carbohydrates
• Isosorbide (1,4:3,6-dianhydro-D-sorbitol)
• Glucose
Glucose – Na+, K+, Cl-
• Glucitol (sorbitol, (2S,3R,4R,5R)-hexane-1,2,3,4,5,6-hexol)
Glucitol – Na+, K+, Cl-
• 1,4-anhydroglucitol (1,4-anhydrosorbitol, 1,4-sorbitan, arlitan)
Chemistry Coverage in the MSEPUB Databank (16)
• Organics and their mixtures with water • Alcohols
Methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, cyclohexanol
• Glycols
Monoethylene (MEG), diethylene (DEG), triethylene (TEG), propylene, polyethylene glycols
MEG, DEG, TEG - hydrocarbons
• Phenols
Phenol, catechol
• Ketones
Acetone, methylisobutyl ketone
• Aldehydes
Butylaldehyde
• Carbonates
Dimethylcarbonate, diethylcarbonate, ethylene carbonate, propylene carbonate
• Halogen derivatives
CCl4, CHCl3, CH2Cl2
Chemistry Coverage in the MSEPUB Databank (17)
• Organics and their mixtures with water
• Aminoacids
Methionine, glycine
• Nitriles
Acetonitrile, 3-cyanopyridine, cis-crotonitrile, trans-crotonitrile, fumaronitrile, acrylonitrile, bis (cyanoethyl) ether
• Amides
Dimethylacetamide, dimethylformamide
• Heterocyclic nitrogen compounds
Oxazole, pyrazole, 3-methylpyridine, pyrimidine
• Esters
Butyl acrylate, butyl 3-butoxypropionate, butyl acetate
• Epoxides
Ethylene oxide
• Oximes
Cyclohexanonoxime
Chemistry Coverage in the MSEPUB Databank (18)
• Organics and their mixtures with water
• Lactams
Caprolactam
• Nitro compounds
Nitrobenzene
• Ethers
t-amyl methyl ether
• Mercaptans
Ethyl mercaptan
• Disulfides
Dimethyl, dipropyl mercaptans
Chemistry Coverage in the MSEPUB Databank (19)
• Lithium salt – organic carbonate systems • LiPF6 – dimethylcarbonate - diethylcarbonate – ethylene carbonate - propylene
carbonate
• LiBF4 – H2O – dimethylcarbonate – ethylene carbonate
• Mixed-solvent inorganic/organic systems
• Methanol – salt systems
Methanol – H+ – Na+ – K+ – Mg2+ – Ca2+ – Sr2+ – Ba2+ – Cl- – CO32- – HCO3
- – SO4
2- – BO2- – HCOO- – CH3COO- – CO2 – H2S
Methanol - O2
• Glycol – salt systems
Mono, di- and triethylene glycols – H+ – Na+ – K+ – Mg2+ – Ca2+ - Sr2+ – Ba2+ – Cl- – CO3
2- – HCO3- - SO4
2- – BO2- – CH3COO- – CO2 – H2S
Glycols - O2
• Ethanol – salt systems
Ethanol – Li+ - Na+ - Cl-
Ethanol – O2
• Phenol - acetone - SO2 - HFo - HCl – H2O, octane
• Phenol - H2SO4 - Na2SO4 - NaOH
Chemistry Coverage in the MSEPUB Databank (20)
• Mixed-solvent inorganic/organic systems
• n-Butylaldehyde – NaCl - H2O
• NH3 – methanol, ethanol, hexane, acetylene, H2
• Cyclohexanonoxime - H2SO4 - SO3
• Caprolactam - H2SO4 - SO3 - (NH4)2SO4 • Mixed-solvent organic systems
• HAc – tri-N-octylamine – toluene – H2O
• HAc – tri-N-octylamine – methylisobutylketone – H2O
• Dimethylformamide – HFo – H2O
• MEG – EtOH – H2O
• Butyl acrylate – acrylic acid – butanol – toluene
• Methanol – hexane, benzene
• Ethanol – hexane, benzene, toluene
• 1-Propanol – CCl4, toluene
• Isopropanol – benzene, cyclohexane, hexane, toluene
• t-amyl methyl ether - toluene
Chemistry Coverage in the MSEPUB Databank (21)
• Polyelectrolytes
• Polyacrylic acid
Complexes with Cu, Zn, Ca, Fe(II), Fe(III)
• Polymaleic acid
• Ionic liquids (cations: 1-ethyl-3-methyl imidazolium (EMIM), 1-butyl-3-methyl imidazolium (BMIM)
• BMIM-N(SO2CF3)2 – H2O, methanol, toluene, hexane
• BMIM-PF6 – H2O, methanol, toluene, hexane
• BMIM-SO3CF3 – H2O, toluene, hexane
• BMIM-BF4 – H2O, methanol, toluene, hexane, CH2Cl2
• EMIM-N(SO2CF3)2 – H2O, methanol, toluene, hexane, CH2Cl2
• EMIM-PF6 – H2O, toluene
• EMIM-SO3CF3 – H2O, methanol
• EMIM-BF4 – H2O, methanol, toluene, hexane
• EMIM-N(SO2CF3)2 – BMIM-N(SO2CF3)2 – H2O
• EMIM-N(SO2CF3)2 – BMIM-N(SO2CF3)2 – hexane
• BMIM-BF4 – BMIM-PF6
Chemistry Coverage in the MSEPUB Databank (22)
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