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One of the main purposes for Minteq type of programs is to perform adsorption
calculations, in addition to doing the straight forward acid-base-complexation-
precipitation calculations in the presence and absence of gas with and without redox
reactions. Often, the most important processes for trace elements are various adsorption
reactions and these reactions are rarely treated in courses or text books, probably because
they tend to be ill defined and there are not as many simplistic descriptions as with e.g.
solubility constants.
Pb2+ OH-
-
OH ≡SOH OH +
+ - H
O- ≡SO- Na Cl -
Cl- HCO 3
OPb+ ≡SOPb+ PbOH+
Often these measured Kd values are used to report data. These Kd values are tabulated for
specific solids and waters, e.g., sea water or lake water, etc., and as long as the overall
conditions of pH, redox, complexing agents, etc., are reasonably constant these Kd values
can be used to calculate the overall concentration in solution from the solid phase value,
or vice versa, and thereby bio-availability to organisms:
Solid metal oxides and other surfaces often are strong adsorbers of aqueous species, such
as Pb2+, PO43-, AsO43-, etc. There are many types of options for adsorption reactions.
Mostly, they divide into three groups.
1. Simple isotherms, illustrated for aqueous cadmium ion activity, {Cd2+}, adsorption
to a surface oxide site, ≡SOH, to for form ≡SOCd+ + {H+}:
a. Linear isotherm: [≡SOCd+]adsorbed = Kads.{Cd2+}
with Kads(L of solution/kg of solid). These Kads. constants are often supplied
by a local curve fitting of the adsorption of some metal onto the overall bulk
solid phase. Visual Minteq permits you to add any Kads. value you wish and it
will then incorporate that Kads. value into an overall speciation with redox,
precipitation, etc., scheme and model the amount of trace metal adsorbed.
This is a very practical and useful option for real site data to account for the
effect of e.g., added complexing agents or changes in pH in the site and still
use the measured Kads.
2. Ion exchange adsorption of ions, for example for Cd2+ exchanging with Ca2+:
[≡SOCa+]adsorbed + Cd2+ Æ [≡SOCd+]adsorbed + Ca2+,
or:
[≡ SOCd + ]adsorbed ⋅ {Ca 2 + }
K ion exchange = ,
[≡ SOCa + ]adsorbed ⋅ {Cd 2 + }
The basic problem will be to describe the adsorption of arsenic, AsO43-, and cadmium,
Cd2+, to “hydrous ferric oxide, Fe(III)Oxide⋅H2O, versus pH and pe and in the presence
of various competing ions, etc., but first the acid/base chemistry of simple hydrous ferric
oxide. We will use 1 g/L at surface area of 100 m2/g and a site density of active ≡FeOH
sites of 1site/nm2 –this is a reasonable, but low sorption condition that might correspond
to ferric oxide in sediment or in water treatment by adding ferric chloride to induce
“hydrous ferric oxide” precipitation and adsorption for arsenic removal. A graphic
representation is as follows from Stumm and Morgan, “Aquatic Chemistry 3rd ed.,”
Wiley, 1996:
σo + σd = 0.00
Almost every text seems to use a different set of units to express surface charge and
related quantities, but Visual Minteq uses the following:
Ordinarily, it would be expected to treat the charge on the surface just like is done
with activity coefficients and ionic strength and use some simple expression to correct
for the surface charge as is done using the Davies or the Debye-Huckel equations.
The problem with this reasonable approach is that practically solids accumulate so
much charge on the surface under some circumstances of pH and ionic strength the
impact on the adsorption or ions can be orders of magnitude in value, but at other
ionic strengths or pH’s it may not too important. All these circumstances are treated
with the electrostatic double layer models used in Visual Minteq (from the Minteq
tutorial on the EPA web site):
≡SOH + H+ Æ ≡SOH2+
and
≡SOH Æ ≡SO- + H+
wherein the ≡SOH refers to the surface metal hydroxide, such as ≡FeOH with
hydrous ferric oxide or ≡SiOH with silica. The effect of the surface charge, ≡SO- or
≡SOH2+, on adsorption is given by a Boltzmann-type factor for activities and in
Visual Minteq it is written as follows:
where z = charge on the ion including the sign, {X sz } = activity of the ion
immediately next to the surface, {X z } = activity of the ion is solution far enough
away to not be influenced by the surface, e −ψ o ⋅ F /( R ⋅T ) = Boltzmann factor, ψ o (Volts)
surface potential relative to bulk solution and may be positive or negative, F =
Faraday constant = 96,500 C/mol, R = gas constant = 8.31 V⋅C/(mol⋅oK) = 8.31
J/(mol⋅oK), and T = oK. Note for reference that the value of the exponential in the
Boltzmann factor, e −ψ o ⋅ F /( R ⋅T ) , is equal to 1.00 for the following common conditions
of 20 oC and a common surface potential of 25 mV (from Stumm and Morgan), -note
that this corresponds to about ½ pH unit:
o o
e − ψ o ⋅ F /( R ⋅T ) = e −[0.025V ⋅96,500C / mol] [8.31VC /( mol⋅ K ) ⋅ 293 K ] = e −1 = 0.37
As the surface becomes protonated, ionizes, or adsorbs charged ions, it obtains some
calculated surface charge, Tσ o , as will be seen below. For a diffuse layer of ions next
to a solid the theoretical relationship between surface charge and surface potential is
given from electrostatic theory by:
Tσ o = 0.1174 ⋅ I1 / 2 sinh( Z ⋅ ψ o / 2 ⋅ R ⋅ T)
at 25 oC with I (M) ionic strength and Z = 1.00. The value of ψ o (V)can be either
plus or minus. The sinh(x) function looks like the following:
5
3.627
sinh( x) 0
− 3.627 5
2 1 0 1 2
−2 x 2
At small values of “±x”, Tσ o ≈ 2.3⋅I(M)1/2⋅ ψ o (V). For example, for an iron oxide
surface with no other adsorbing ions the surface charge is calculated from the surface
speciation:
+ -
Tσ o = [≡FeOH2 ] - [≡FeO ] Net surface charge.
The mass balance for all surface sites, Tot≡FeOH, would be:
In Visual Minteq the reference component for surface sites is always the neutral
species, [≡FeOH], generally written as [≡SOH]. The equilibrium constant for the
formation of [≡FeOH2+] and [≡FeO-] are as follows in Visual Minteq terminology in
terms of components, [≡ FeOH] and {H + } and [e −ψ o F / RT ]+1 :
≡FeOH + H+ Æ ≡FeOH2+
as seen in the following screen from Visual Minteq. It should be noted that the {H+}
term refers to the normal aqueous hydrogen ion activity which is the concentration
times the activity coefficient, {H+} = [H+]⋅ γ H + , which the program calculates. For
mathematical simplicity the Boltzmann factor term is treated as an explicit
component and given a name, Psio1, in Visual Minteq. This is illustrated in Visual
Minteq (details of how to open this screen will be listed below):
In summary, surface ionization and complexation is treated exactly like any other
acid/base or complex species in solution, except that the Boltzmann correction term
must be solved simultaneously with the sinh(…) term, similar to the activity
coefficient in solution and the Davies equation. Even though this complicates the
algebra, it adds nothing new to the formulation of a problem.
f. Click the X! button with the Site Conc. space empty and the program calculates
the Site conc. (low affinity; mmol of sites/l) = 0.166 mM low affinity sites. This
means that with this solid concentration the surface is the same as having
0.166x10-3 M in solution for titration, etc. We normally just use the low affinity
sites, the high affinity sites are given used to model some systems and are
designated, ≡FehOH, etc. It is important to note that for the X! button to work,
the Site Conc. field must be blank!
h. The following will appear and double click on the file, feo-dlm.mdb:
This tutorial will use this data base, feo-dlm.mdb, to illustrate the methods, but the reader
is encouraged to open and examine the various other data bases and examine the Minteq
tutorials for explanations of the various details and assumptions.
i. Click on Edit sorption … button and scroll down and click on ≡FeOCd+ species
and the following will appear:
with Keq = 10-2.9 this is the expression represented in the above screen image for the
species ≡FeOCd+.
Again, unless it is necessary to change these values or to add equilibrium values not
listed in the data base, it is not necessary to do anything; when you choose a
component from the list on the Main Menu or you add solid phase, etc., all
equilibrium related to that component and solids will be automatically included.
Click on Quit and then Save and Back to Main Menu and the adsorption data base
will be automatically included in all calculations.
Back at the Main Menu, click on “View/add edit” and the following will appear:
This Output screen says that 1 g/l of hydrous ferric oxide with 100 m2/g surface area
and 1 site/nm2 on the surface when added to water with 0.01 M ionic strength will
have a pH = 8.015, a value of Psio1 = 0.0048 and surface charge of 0.00111 C/m2.
Adsorption 2 HFO low ionic strength.VDA Alternatively, if you had selected the
Calculate Ionic Strength option on the Main Menu, the pH = 7.117, etc…
d. Set ionic strength to 0.001 M and click on Run Minteq, selected sweep results on
the output menu, print to Excel and after a little plot formatting:
1.E-02
[≡FeOH2+] = [≡FeO-] is at
1.E-03
1.E-04
about 8.1 pH, as expected
1.E-05 from other sources such
1.E-06 zeta potential, and from
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 (pK1+pK2)/2 =
(7.29+8.93)/2 = 8.11. The
pH
unusual thing to note about
>FeOH2+ (1) >SOH(1) >FeO- (1) this curve compared to the
corresponding log C vs. pH
curve for weak acids with the same pK-values is the exceptionally wide range over which
[≡FeOH], the neutral species, is the predominant species –from about 4 pH to 12 pH.
Since the corresponding dibasic acid would have had pK1 = 7.29 and pK2 = 8.93, the
middle species, [≡FeOH], would be predominant from pH = 7.29 to pH = 8.93. The
surface potential is the difference: at low pH values the positively charged surface repels
the solution H+ causing the apparent ionization constant (i.e., where [≡FeOH2+] =
[≡FeOH]) to be about pKapparent,1 ≈ 4.0 versus 7.29. At higher pH’s the opposite happens,
1.E-03
1.E-04
1.E-05
1.E-06
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
TotCd(aqueous), M
1.E-06
1.E-08
1.E-10
1.E-12
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Notice that the cadmium is adsorbed but only above about 7 to 8 pH. At higher pH
values, the hydrolysis of Cd2+ to form hydroxide complexes increases the solubility.
1.E-04
1.E-05
1.E-06
1.E-07
1.E-08
1.E-09
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Cd+2 Series2
AsO4-3 H3AsO3
a. Set the pe value at –3.0 by selecting the Parameters then Specify pe and Eh:
b. Select Fixed pe and enter “–3” as follows and then Save and back to main menu:
c. Include the redox couple between AsO43- and H3AsO3 by selecting Redox menu
and add the H3AsO3/AsO4 redox couple as follows and select Add and back to
main menu. Select Run Minteq.
1.E-06
1.E-08
1.E-10
1.E-12
1.E-14
1.E-16
1.E-18
1.E-20
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
AsO4-3 H3AsO3
d. Select the pH sweep from 0 to 14 pH and the output of Total Dissolved for each
component in Excel will look something like this after some rearrangements.
First for specific pH = 9.0 and then for pH sweep.
Apparently, the minimum Total As conc. occurs at about 8.5 pH where from the above
plot output screen TotAs(III) ≈ TotAs(V) ≈ 3E-9 M ≈ 0.2 ppb TotAs dissolved in
solution. The present EPA standard is 50 ppb and that will be reduced to 10 ppb in 2006.
Alternatively, if the pH is 8.0 instead of 9.0, the TotAs conc. is about the same, but the
predominant form is As(III) which is by far the more toxic of the two forms.
At 8 pH: