Brief update: Visual MINTEQ modeling

effort (and writing)

CCM model for Ga-kaolinite adsorption

• Permanent sites: ≡X-

• Basal siloxane grps, ionic exchange occurs here (Si)
• Variable charge sites: ≡SOH
• On mineral edges, complexation occurs here (Al, Si)
• Gu & Evans, 2008 uses the CCM model for edge grps Charge sites on 2-site adsorption model (Gu & Evans, 2008)
• Assumes all surface species are inner sphere, constant IS
• Assumes a linear relationship between surface potential (ψ)
and charge density (σ) at constant capacitance (κ) (σ=κψ
• Critical parameter is surface site density which can be found
from adsorption experiments
• Gu used CEC at pH=8 as a measure of total site density
• Using titration data, best fit 6:1 ratio of ≡SOH : ≡X-
CCM rxns and adsorption mechanisms considered
•1)  Inner-sphere complexation (basal groups)

2) Inner-sphere complexation (edge groups)

Charge sites on 2-site adsorption model (Gu & Evans, 2008)

M = adsorbate cation, m+ is its charge, S is the
cation in mineral functional groups (Al, Si, etc)
Visual MINTEQ: model adsorption with a mineral
• Specify finite solid phase (mineral) after inputting general system inputs and constraints (components,
concentrations, pH range, “problem” specifications, etc).
 Visual MINTEQ: combine 2 models into one

• Modeling Ga - kaolinite adsorption requires a 2-site model

1) Basal groups (ionic exchange)
2) Edge groups (inner-sphere complexation)
• After solid phase added (prev. slide), surface complexation model
can be configured from top menu
• Number of surfaces is 1
• Can incorporate ionic exchange into any model
• Ionic exchange: “Fixed charge site”
• Surface complexation: “2-pK CCM”
• Select counter-ion accumulation or the model does not consider
ionic exchange
Visual MINTEQ: CCM
database
•  CCM complexation reactions

Update logK for these rxns with kaolinite

• Last reaction for Ga:

• Add =SOGa as a species to complex DB?

Doi et al., 2020

Next steps
• How to incorporate ion exchange reactions considered in Gu & Evans, 2008
• Current DB doesn’t have Si species (has Al), but ion exchange occurs on basal “siloxane” grps: does it matter? Does
this DB require changes?
• Does the CCM complexation DB require additional reaction edit
• For the rxn between surface functional group (=SOH) and Ga
• Or does the program compute this reaction by itself based on presence of Ga in the initial problem?
• If a new reaction must be added, must calculate the logK for this rxn using the expressions cited by literature
(Goldberg, 1992, Doi et al., 2020, Gu & Evans, 2008, etc.)
• Component and species matrix as per Doi et al, 2020
• How is this matrix input? By the CCM database components or another way?
• Experiment with the model more, try to find the answers to these questions and read more