# Presentation: 223392

## Fluid Properties for New Technologies:Electrolyte Systems

**Andrzej Anderko**
**OLI Systems, Inc.**
- 108 American Road, Morris Plains, NJ 07950

**Notes:**
Self-diffusivity
Page 1 of 17

## Technologies of interest

**Thermophysical**
**properties and**
**chemistry of **
**electrolytes**

**Process Simulator Interfaces**

**ESP**
**Environmental**
**Simulation**

**Flow Assurance SW**
**Upstream Scale/**
**Corrosion/Production Chem**

**CSP**
**Corrosion**
**Simulation**

**CrySP**
**Crystallization**
**Simulation**

## Technology highlights

- From electrolyte thermodynamics to corrosion simulation: Importance of the properties of electrolyte systems
- Fluid properties for supercritical water oxidation
- Electrolyte properties for designing syntheses of inorganic materials
- Soil/aqueous systems: Combined effects of adsorption, solubility, phase splitting, etc.
- Database needs

## Prediction of corrosion: Role of thermophysical properties

- Thermodynamic equilibrium calculations
- What species exist in the system?
- What are the activities of corrosive species?
- Computation of transport properties
- Diffusivity and viscosity are necessary to model processes related to the mass transfer of species to and from a corroding interface
- Thermodynamic and transport properties are used as input to electrochemical kinetics models

## Prediction of corrosion: Role of thermodynamic properties

***Example 1: ***Corrosivity of acids depends on the activity of protons
***Example 2: ***
- Anhydrous HF is not corrosive
- Aqueous HF is very corrosive
- Transition between the two regimes depends on thermodynamic speciation

- HCl

- H2SO4

- H3PO4

## Properties for supercritical water oxidation

***Problem:*** Precipitation of salts limits the operation envelope
- Other properties (VLE, densities, enthalpies) are also needed

- NaCl + H2O

## Properties for supercritical water oxidation

- Methodology:
- Computation of vapor-liquid and solid-liquid equilibria
- Kinetic modeling of oxidation processes
- Current status:
- An accurate equation of state is available, but it has been parameterized for a limited number of systems
- Limitations:
- Lack of phase equilibrium data for many systems
- Behavior of multicomponent systems is poorly known
- Little is known about transport properties, especially in the presence of salts

## Properties for designing syntheses of advanced inorganic materials

***Example:*** Hydrothermal synthesis of ceramics: precipitation of multicomponent oxides from complex aqueous systems
***Problem:***
-     How to optimize the conditions of the synthesis?

## Properties for designing syntheses of advanced inorganic materials

- Methodology:
- Equilibrium computations for multicomponent electrolyte systems with multiple competing solid phases
- Current status:
- Syntheses of several piezoelectric ceramics have been successfully optimized and implemented
- Limitations:
- Lack of thermochemical data for many complex solids (e.g. multicomponent oxides) and secondarily, aqueous species
- Insufficiently advanced methods for estimating thermochemical properties

## Soil/Aqueous Systems

- Methodology:
- Adsorption phenomena (ion exchange, molecular adsorption, surface complexation)
- Phase equilibria in the bulk (e.g., partitioning between aqueous and NAPL phases)
- Solubility and speciation effects in the aqueous phase
- Current status:
- A comprehensive model has been developed and verified against experimental data
- Limitations:
- Parameters cannot always be determined because of insufficient characterization of systems of interest
- Kinetic effects are not well characterized

## Database needs for mixtures

- Comprehensive, computerized collections exist for nonelectrolyte systems (Dechema, TRC)
- Several printed data sources exist for electrolyte systems at “normal” conditions. However,
- No computerized collection is available
- Many valuable sources have not been updated in decades
- No database exists for high-temperature and supercritical electrolyte systems