Hydrolab on advanced hydrogeochemistry

Part (1)

1) Find the pH of solutions with the following [H+]. Classify each as acidic or basic.

a) 0.33 M, b) 4.6 x 10-8 M, and c) 7.2 x 10-14 M

2) As part of your routine monitoring tasks, you take a 2 L sample from a lake and measure an
electrical conductivity value of 2.50 mS/cm. On the way to the lab you stop by at the office to fetch
some documents. While in the office, your colleague with whom you have an antagonising
relationship seizes the opportunity and drops 1g of table salt into your sample. Using an EC/TDS
conversion of 0.6, answer the following questions:

a) How much (in percentage) has the EC of your sample changed?

b) What, if that scumbag of a colleague had used 1g of sugar instead of table salt, what would have
been your new EC (in microS/cm)? Assume sugar is glucose with the formula C6H12O6 and a FW of
180 g/mol.
c) There is one VITAL physico-chemical parameter missing in this exercise to estabish a
meaningful value of the change in EC, apart from the addition of salt/sugar, which one is it?

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(2) Mineral Precipitation and Dissolution

Revision. Consider the reaction

a A + b B = c C + d D.

The solubility product is the theoretical value of K, the equilibrium con-

stant, for sparingly soluble materials. So, for the reaction above,

{C}c {D}d
Ksp = (1)
{A}a {B}b

Note the exponent is the stoichiometric coefficient, and that the curly

brackets indicate activity, which for your purposes can be considered as

equal to concentration in moles litre−1 . The activity of pure solids, liquids,

and gases can be taken to be 1.

The ion activity product KIAP is the observed value of K, and may be

different to Ksp if the solution is out of thermodynamic equilibrium, or if

the solution is undersaturated with respect to the solid phase considered.

Undersaturated means that the mineral would dissolve it were present. If

KIAP < Ksp for a particular mineral then the solution is undersaturated,

and if the mineral is present then it will dissolve if kinetics allow. If, on

the other hand, If KIAP > Ksp then the solution is oversaturated with

respect to that mineral, and the mineral will precipitate if kinetics allow.

A useful way to compare KIAP and Ksp is via the saturation index (SI ).

The definition of which is:

SI = log10 KIAP − log10 Ksp (2)

If SI is positive, then the mineral will tend to precipitate, and if SI is

negative then the mineral will tend to dissolve. If SI is zero then the

solution is in thermodynamic equilibrium with respect to the mineral of

interest and it will neither dissolve or precipitate.

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(a) The solubility product, Ksp , for quartz is 10−3.98 , with reference to

the reaction

SiO2 (s) + H2 O (l) = H4 SiO4 (aq)

The observed concentration of H4 SiO4 (aq) in a sample is 3 mg litre−1 .

(i) What is the concentration of H4 SiO4 (aq) in moles litre−1 ? The

atomic mass of H is 1, of Si is 28, and of O is 16.

(ii) What is KIAP for the reaction SiO2 (s) + H2 O (l) = H4 SiO4 (aq)

in this solution?

(iii) What is the SI for quartz in this solution?

(iv) Is quartz likely to precipitate from, or dissolve into, this solu-

tion?

(b) The solubility product, Ksp , for anhydrite (CaSO4 ) is 10−4.36 , with

reference to the reaction

CaSO4 (s) = Ca2+ (aq) + SO2−

4 (aq)

The observed concentration of Ca2+ (aq) in a modified seawater is 412

mg litre−1 and the concentration of SO2− −1

4 (aq) is 2712 mg litre .

(i) Write out the expression for K for this reaction.

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 (ii) What are the concentrations of Ca2+ (aq) and SO2−
4 (aq) in moles

litre−1 ? The atomic mass of Ca is 40.1, of S is 32.1, and of O is

16.

(iii) What is KIAP for the reaction CaSO4 (s) = Ca2+ (aq) + SO2−
4 (aq)

in seawater?

(iv) What is the SI for anhydrite in this solution?

(v) Is anhydrite likely to precipitate from, or dissolve into, this so-

lution?

(c) The solubility product, Ksp , for gibbsite (AlOH3 ) is 1010.8 , with ref-

erence to the reaction

Al(OH)3 (s) + 3 H+ (aq) = Al3+ (aq) + 3 H2 O (l)

The observed concentration of Al3+ (aq) in a sample of minewater is

0.72 mg litre−1 and the pH is 3.

(i) Write out the expression for K for this reaction.

(ii) What is the concentration of Al3+ (aq) in moles litre−1 ? The

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 atomic mass of Al is 27 g mole−1 .

(iii) What is the activity of H+ (aq)? Remember pH = -log10 {H+ }.

(iv) What is KIAP for the reaction Al(OH)3 (s) + 3 H+ (aq) = Al3+ (aq)

+ 3 H2 O (l) in this minewater?

(v) What is the SI for gibbsite in this solution?

(vi) Is gibbsite likely to precipitate from, or dissolve into, this solu-

tion?

(3) Geochemical Modelling

As you have seen, or are about to see, calculations of mineral solubility

and solute speciation are time-consuming and can become complex even

in relatively simple systems. For this reason, geochemical calculations are

often undertaken on computers. Today you will have a brief introduction

to PhreeqC, a program written and distributed by the USGS (United

States Geological Survey), that is used widely to interpret and predict

the characteristics of surface and groundwaters. PhreeqC can be obtained