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Tutorial On Visual Minteq 2.30 Intro Acid-Base PDF
Tutorial On Visual Minteq 2.30 Intro Acid-Base PDF
To install Visual Minteq click on the following and follow the instructions:
http://www.lwr.kth.se/English/OurSoftware/vminteq/#download
Generally, it is recommended that you work problems that you are already
familiar with, to see how the program works –open all the buttons and windows with a
known problem, for example the pH of 0.001 M NaH2PO4 in water at 25 C is 5.13,
neglecting activity coefficients. The layout of the program is based around the
“component” concept, e.g., TotPO4 plus the notion of the TotH (proton balance
condition) for the solution, but you may alternatively use the mass balance plus the
charge balance approach to solve all problems; understanding the difference is one the
main sources of confusion using Visual Minteq and related software. You can calculate
the pH via mass balances (combine TotPO4 plus TotH) or via mass balances (TotPO4)
plus the Charge balance condition {Sum(cations) - Sum(anions) = 0.00}.
At a theoretical level it can be shown that the two options are equivalent, but at a
practical level they appear to be quite different. Although Option 2 is often more
intuitive for students, it should be noted that the Option 1 is often tens to hundreds of
times faster to converge and it is clearly the preferred method of professional
programmers. If you enter all the components of a solution such that the solution is
electrically neutral (e.g. a solution contains only 0.001 M Na3PO4 or 0.001 M Na2HPO4),
i.e., actually how it is prepared so that all anions are counterbalanced by cations, then the
two methods of calculation will always yield the same result, although the practical input
data is often different, as will be illustrated.
First, we will solve a set of problems based around a solution that is 0.001 M TotPO4.
Later we will add PCO2, after we learn how to enter data and interpret the output and then
do titrations. This problem is similar to Prob. No. 4.46 in Sawyer, McCarty, and Parkin,
Chemistry for Environmental Engineers, 5th” McGraw Hill, 2003. Initially, we will
work this problem several ways to better understand how the program options works and
the meaning of the various Output boxes.
One way to look at solving problems in Visual Minteq is to use the “Calc. from mass
& charge balance” option, Option 2, all the time. This is likely more intuitive and in
keeping with the overall theme in many text books. The key to remember in using this
option is that in Visual Minteq using the pH “Calc. from mass & charge balance”
option, it is always assumed that the TotPO4, etc., can be viewed as having been added as
the fully protonated acids, H3PO4, H2CO3, etc., to which strong bases (e.g., Na+, Mg2+, or
Ca2+ as NaOH, Mg(OH)2, or Ca(OH)2, etc.) and strong acids (such as Cl-, NO3-, or SO42-
as HCl, HNO3, or H2SO4, etc.) are added to make a solution to a given pH. In this
approach you do not use the TotH concept, although the program will still calculate TotH
1. Given a set of neutral compounds added to water, calculate the pH (for example,
0.001 M Na2CO3 plus 0.001 M NaOH or 0.001 M HAc);
2. Given total component concentrations and measured or assumed pH, calculate the
species (such as, at 8.1 pH and TotPO4 = 0.001 M);
3. Given the solution composition and pHinitial, calculate the acid or base to change
the solution to a second pH, pHfinal (such as, initially TotPO4 = 0.001 M and
pHinitial = 8.10, calculate the amount of strong acid needed to lower the solution to
pHfinal = 6.00);
4. Given a solution composition, calculate the titration curve (e.g., calculate the
titration curve of 0.001 M K2HPO4 with 1 M HCl acid); and
5. Given an pHinitial and the solution composition, calculate the titration curve of the
solution (given pHinitial = 8.1 with TotPO4 = 0.001 M, calculate the titration curve
upon addition of acid or base.)
First, an example of each problem type will be solved step-by-step and then a bit of
background discussion and comparison with the “mass balance” only approach will be
presented. Input files with corresponding names are attached, but they must be saved in
the C:\vminteq\ folder, such as: “C:\vminteq\ Example 1a calc pH.VDA” for the first
example. To run the corresponding input file: On the main menu screen click File, Open
Input file, scroll down to the file name, click on the file name, select open to open the file
and return you to the main menu, click on Run MINTEQ.
1 a. Example 1a calc pH.VDA. Given a set of neutral compounds added to water,
calculate the pH (0.001 M Na2CO3 plus 0.001 M NaOH, calculate the pH);
1. Open Visual Minteq software, everything is initialized;
2. pH box click “Calc. from mass & charge balance”;
3. Ionic strength equal 0.00; units Molality;
4. Component window select CO3; and concentration to 0.001 M;
5. Units Molality (m) ≅ Molarity (M) to within about ± 0.3 % for most solutions
and the difference is never of concern to us in any practical problems;
6. Click “add to list”;
7. Component window select Na+; and concentration to 0.003 (i.e., 0.001 +
0.002 M);
8. Click “add to list”;
9. Click Run Minteq and then OK and you are taken to the Output screen:
and observe that the TotCO3 = 0.001 M, TotNa = 0.003 M, and that TotH = -
0.001 M. The negative value of TotH means that there is an excess of OH- added
equal to the concentration of NaOH. As a component the way to add an excess of
OH- is to add a negative value for TotH. This can be done by selecting H+ and
typing –0.001 in the Total concentration bar on the main menu:
Notice the dual use of the same symbol, “H+1”, to refer to the concentration of
free hydrogen ions in solution, [H+1], as related to pH in the Output screen and to refer to
the total concentration of the component hydrogen added to solution, TotH, in the
Component screen and on the main menu input. This dual use of the same symbol is a
common source of confusion.
1. Click on Parameters then Various default settings in the main menu and select
the yes button next to Show organic components and then Save and quit:
2. Select Component name box and the following will appear. Set Acetate-1 to
0.001 M.
For example: [PO4-3] = 4.7174E-08 M from the Output menu and note that the
Concentrations and activities are the same since we set ionic strength to 0.00. It
was not necessary to choose the method to calculate pH, because pH was
specified. Since the sum of anions is 1.89 mM greater than the sum of cations, to
prepare 0.001 M TotPO4 with a pH = 8.10, one could add 1.89 mM strong base
8. Select titration box and click on the “go to titration manager” bar;
9. Click the Titration box, put 40 in no. of titration points, make volume = 1.00 L
and volume of titrant = 0.0001 L (0.1 ml and 0.1 meq./L);
10. Click the box “Start addition on the 2nd step”, this gives you the pH, etc. at the
start of the titration;
11. Type 1.00 in Concentration box and select H+1 and click on “Save and Next” and
select Cl-1 and “Save and Next.” This will add 1/10th of a milli-equivalent of HCl
per titration point. Since most solutions are in the range of about 1 to 3 milli-
equivalents of weak acid, this will normally give a nice looking titration curve.
Adjustments can be made to give finer looking titrations.
18. Plot the data against Cl-1, amount (M) of HCl added. Again, notice that the line
labeled “H+1” is actually the TotH value that starts at TotH = 0.001 M. If in the
titration sweep window we had selected “H+1 concentration,” instead of “H+1
Total dissolved” we would have gotten [H+]=10-pH. Since this is the titration
curve of 0.001 M K2HPO4, there is an inflection point at 0.001 M HCl added at
pH ≈ 5. There is not a second inflection point at 0.002 M HCl because the first
ionization constant of phosphoric acid is K1 ≈ 10-2 which is moderately strong
acid compared with the concentration of TotPO4 = 10-3 M.
10 0.006
8 0.005
0.004
6 pH
0.003
4 H+1
0.002
2 0.001
0 0
0 0.001 0.002 0.003 0.004 0.005
10 0.006
8 0.005
0.004
6 pH
0.003
4 H+1
0.002
2 0.001
0 0
0 0.001 0.002 0.003 0.004 0.005
This plot can also be used to calculate the amount of acid or base to go between
any two pH values from 8.100 and below.
6. Click Run Minteq and then click on OK and the output window will automatically
open:
8. If you click on Display saturation indices, the screen will be blank, because no
minerals are possible. Click on Equilibrated mass distribution:
with
[H ]3 ⋅ [PO 34− ] [H]2 ⋅ [PO 34− ] [H ] ⋅ [PO 34− ] K
[H 3 PO 4 ] = , [H 2 PO 4− ] = , [HPO 24 − ] = , and [OH - ] = w
K1 ⋅ K 2 ⋅ K 3 K 2 ⋅ K3 K3 [H + ]
The species are given below, as copied to Excel from the output file is:
The value of TotH (Sum of protons gained minus the sum of protons lost, i.e., proton
balance, or TotH) is zero to within convergence error, either from the above Excel
addition or from Visual Minteq “Equilibrated Mass Distribution” window TotH = -
4.1372E-12 –when I transferred data from the Output screen to Excel and re-added
them the sum was -2.38E-09, which is round off difference in the copy and transfer,
As can be seen from the top of the “Output” window, the solution is not electrically
neutral. That is to say, this solution can not be made up as simply phosphate, PO43-,
into water. If you added Na+ = 0.003 M as another component, you will get the same
answer, except that the solution will be electrically neutral, and the % Charge
difference box would be 0.0000 %. Try it. Also, if you select H+ on the Main menu
in the components box and make the concentration 0.003 and click on Add to list:
and click on Run the pH = 3.051, the pH of 0.001 M phosphoric acid in water since
TotPO4 = 0.001 and TotH = 0.003.
Try it.
7. Example 7 mass and charge balance.VDA. Next, solve the same problem with the
same input data with pH “Calc. from mass & charge balance” selected:
As you can see, since the charge balance equation has no strong acid anions, e.g.
NO3-or Cl-, and no strong base cations, e.g., Na+ or 2⋅Ca2+, it is the same as having
added 0.001 M H3PO4 to the solution and then calculate the pH, pH = 3.051. Note
also that the TotH component calculation, reported in the Equilibrated Mass
Distribution window is TotH = 1⋅[HPO42-] + 2⋅[H2PO41-] + 3⋅[H3PO4] + 1⋅[H+] -
1⋅[OH-] = 0.003000 M, although this equation was not used in the calculation,
because the charge balance option was selected and no strong base cations, Na+, were
added. If you add 0.003 M Na+ to the component list on the Main menu, and use
Charge balance option to calculate the pH you will get pH = 10.978, as before. Try
it.
8. Example 8 Fixed pH. Commonly, as with a water analysis, you don’t know all the
other strong base cation and anion concentrations very well, but you have a measured
pH value. At this point you enter a fixed pH in the pH box of e.g. 8.10 pH. Then
The program will automatically open the Output Window and there are several things
to note in the top boxes in the Output window: the pH = 8.100; Ionic Strength = 0.00;
number of iterations = 0; sum of cations = 7.9433E-09 moles of charge/kg water (1
L); sum of anions is = 1.8900E-03 moles of charge/kg water; % dif. in cations vs.
anions is 99.999159 %. What the computer solved was the mass balance equations
for total phosphate, TotPO4, using the 8.100 pH. After substituting in the equilibrium
constants, the free [PO43-] concentration is calculated –see equations listed above:
⎧⎪ H3 H2 H ⎫⎪
[PO43-] = 0.001 ⎨ + + + 1⎬ = function of only pH
⎪⎩ K1K 2 K 3 K 2 K 3 K 3 ⎪⎭
The charge balance is not used, but it is computed from the above and reported at the
top of the Output menu and this is often valuable in various calculations.
This means that to prepare a solution of TotPO4 = 0.001 M at pH = 8.100, you would
have to add 0.00189 M Na+ or K+, etc., positively charged strong base cations to the
solution, e.g., as 0.00189 M NaOH or KOH to a solution of 0.001 M H3PO4. You
could write the formula as follows: 0.001 moles of Na1.89H1.11PO4 per liter. Most
likely, what you would have done was to add 0.001 moles of H3PO4 plus 0.00189
moles of NaOH per liter, at this point the net TotH = 0.00111 moles of H+ plus
0.00189 moles of Na+. See next section for verification.
11. Example 11 titration.VDA. Use the calculate pH from “Calculated from mass
balance” option, first:
n. Add “Total dissolved” Cl-1 and H+1, as below (the total dissolved option
includes the concentrations of titratnt that form complexes, in solution and is
generally what you want to use):
Plot the titration against Cl-1. In the Excel Sheet delete the second row and select
and move the pH data to the right of the H+ column.
10 0.006
8
calculated
TotH, M,
6 0.004 pH
pH
4 0.002 H+1
2
0 0
0 0.0005 0.001 0.0015 0.002
HCl M added
The pH “Calculated from mass balance” and the “Calc. from mass & charge
balance” options will both work the same since the initial solution was made to be
the actual solution by initially adding TotH = 0.00111 M and TotNa = 0.00189 M.
The “Calculated from mass balance” used the TotH equation and added 0.0001 M
H+ to each point and calculated the pH. The “Calc. from mass & charge balance”
option added 0.0001 M Cl- to the charge balance equation each time and calculated
the result, this method is much slower to converge and a couple of the points in latter
part of the calculation may not converge completely and might be marked, but they
will be very close. Try it.
12. Example 12a(b) titration with PCO2.VDA. Repeat the titration of 0.001 M
TotPO4 starting at 8.100 pH, but include PCO2 = 0.0005 atm.
7. This is Example 12b. Select Na+ and set concentration to 2.8539E-03 M and click
add, This is the amount of net Na+ to make the solution charge balanced at the
starting point.
8. Select pH box “Calc. from mass & charge balance”;
9. Select Cl- and set concentration to 1E-8 and click add –this will make the Cl- ion
available to you to output the value of Cl- in the titration (quirk of program), as
before;
10. Select tool bar Multiproblem/sweep and set the titration up, as above;
11. The Output menu will appear. Note that the speciation for the 1st titration point
will be shown in the output screen; you can scroll down in the “Select problem
No.” box at the top middle and any of the 40 iteration points will be displayed.
Select Sweep output and print to Excel. The following is the plot after a little
editing and putting TotCO3 and TotH on the secondary axis, as before.
This is Example 13a. The following is the corresponding input into Visual Minteq,
using the left-most analysis and note that input concentrations have been input as
mg/l. The pH of 8.68 is used as a fixed pH and ionic strength has been calculated.
SiO2 is increased by the ratio of H4SiO4(96.1 g/mol)/SiO2(60.1 g/mol) since input is
as H4SiO4, not SiO2; TotCO3 input is as CO3 = 73 mg/l⋅{CO3(60 g/mol)/HCO3(61
g/mol)} + 6 mg/l = {71.8 + 6 mg/l} = 77.8 mg/l as CO3. Iron was assumed to be
TotFe(III) since the solution is probably aerated, but the results would not change
The ionic strength is 4.3 mM, which would correspond to 251 mg/l as NaCl vs. the
observed value of 222 mg/l TDS, which is reasonable. The close agreement between
sum of cations and sum of anions is excellent and may suggest that they adjusted the
charge balance by adding Na+ or K+ to match or that the analyses are exceptionally
good –in either case the analysis is quite self consistent.
Note that TotH = 1.2537E-03 is calculated, which is the proton balance of all species
relative to the Component that was entered.
This is Example 13b. Next, it is often necessary to raise the pH to some value to
precipitate the hardness ions, mostly TotCa and TotMg, and this is illustrated below
by allowing possible solid precipitates of Calcite (CaCO3), Brucite (Mg(OH)2), and
Ferrihydrate (Fe(OH)3). On the main menu Click on Solid Phases and Excluded
Species, Specify possible solid phases, then select calcite, brucite, and ferrihydrate.
Then, on the main menu select Run:
This is Example 13c. By keeping the “Possible solids to precipitate,” as above, and
performing a pH sweep from 7 to 12 pH would produce the following equilibrium
amounts of solids left in solution vs. pH.
1.E-02 1.E-07
1.E-03 1.E-08
1.E-04
1.E-09
1.E-05
1.E-06 1.E-10
1.E-07 1.E-11
7 8 9 10 11 12 13
TotCa+2 TotMg+2
TotCO3-2 TotFe+3SecAxis