Determination of water hardness, and planning calcite dissolution for

stabilizing soft water

Note, as part of the required preparation to this lab, each pair should make the following

calculations and hand in the results to the lab TAs before the beginning of the lab:

Use the stasoft4 software to determine the required strong acid (H2SO4) dosage (prior to

introduction to the column), and the required strong base (NaOH) dosage to the mixed stream

in order to reach the predefined water quality.

Finally, calculate the required volumes of DIW and calcite reactor effluents.

These requirements are explained in the following lab procedure.

Determining water hardness

Water hardness is defined as the sum of all multi valent cations present in the water. It is usually

expressed in mg/l as CaCO3 units. In natural water (and desalinated water) calcium and

magnesium are usually the dominant components of hardness, thus, one can calculate the total

hardness (TH) of the water based on their concentrations. TH can be measured via volumetric

titration with a calibrated solution of Ethylene Diamine Tetra Acetate – EDTA (Na2[H2Y]). In

basic conditions (pH>10) EDTA forms stable complexes with calcium and magnesium ions.

Ca+2 + Na2[H2Y] → [CaY]-2 + 2Na+ + 2H+

The basic pH is maintained by adding a buffer solution. The indicator of the reaction is

Eriochrome Black T (EBT), which has a bluish color. At the beginning of the titration,

magnesium ions found in the water sample form a red complex with the indicator. Addition of

EDTA gradually binds them to form a colorless complex. Once all the free ions are "captured"

by the EDTA, the ions bound to the EBT are released from the unstable complex, changing its

color to blue and indicating the endpoint of the titration:

 Mg+2[EBT] + H2Y-2 → [MgY]-2 + EBT + 2H+

Red Blue

Determination of calcium ion concentration

Ca2+ concentration is determined at pH12, after the precipitation of Mg+2 as Mg(OH)2(s).

Elevating the pH is performed by adding NaOH. After Mg2+ had precipitated as Mg(OH)2 (s) it

no longer binds to EDTA. The indicator of the Ca2+ titration is HNB-Hydroxynaphtol Blue,

which forms a red-purple unstable complex. Once all the free Ca2+ is "captured" by the EDTA,

the HNB bound ions are released, changing the color of the solution to a bluish color –

indicating that the HNB is free of Ca+2 and symbols the endpoint of the titration.

Determination of magnesium ion concentration

After determining the TH and the Ca2+ concentrations, one can calculate from these two values

the Mg+2 concentration:

Total Hardness = [Ca2+] + [Mg2+]

Where, all concentrations are expressed in "mg/L as CaCO3" units. The magnesium

concentration can be isolated from this equation:

[Mg2+] = Total Hardness – [Ca2+]

In order to determine [Mg2+] in M units, the following unit conversion is applied:

[𝑀𝑔 ] =
∙

Where, TH and [Ca2+] concentrations are in "mg/L as CaCO3" units, while [Mg2+] in M units.

Another unit conversion can be done by multiplying the molar concentration of magnesium by

its molecular weight (i.e. 24.3 mg/mmol)

 3 6
NaOH Stabilized
CO2 (?)
water
4

By pass water
70% - 82%
2
CaCO3(s)
dissolution
reactor

1 H2SO4
to pH~2 % split (18 – 30) Soft water from
RO

Figure 1: the post treatment process performed in Ashkelon and Palmachim desalination plants,

Israel.

Soft water stabilization

Figure 1 shows a typical post treatment process (applied in various desalination plants). The

process comprises H2SO4 dosage, calcite dissolution, mixing the untreated stream with the

treated one, and strong base dosage (to the mixed stream) for producing a predetermined water

quality. The process is aimed at elevating the Ca2+ and alkalinity concentrations of the water,

as well as its pH and CCPP values.

Prior to calcite (CaCO3(s)) dissolution acidification of the soft water is required, in order to

enhance the dissolution kinetics and also to enable dissolution of high concentrations, therefore

enabaling applying the process on a small fraction of the water, while bypassing the rest of the

flowrate. Thereafter, the two streams are mixed, and pH adjustments via strong base dosage

(NaOH) is applied for attaining the predetermined water quality (alkalinity, pH, CCPP and

[Ca2+]).

In the lab, deionized water (DIW) represents the soft water or the permeate of a reverse

osmosis (RO) desalination process. Assume that the TDS of the DIW is zero.

Lab protocol

The lab comprises two parts: (1) Stabilization of soft water, including analyzing the stabilized

water; and (2) Analysis of tap water for its TH, Ca2+ and Mg2+ concentrations.

A. Stabilization of soft water

Deionized water is provided to each group. This water will be stabilized using a process

shown in Figure 1. Each group will receive slightly different split flow to be simulated, that

is, the volume (or flowrate) of water destined to pass through the hardening column out of the

overall desalinated water volume (or flowrate). In addition, different target water quality are

given to each group. That is, each group will be given target values of alkalinity, calcium

concentration and CCPP in the product water (see table at the end of the instruction section).

This target quality will be attained by conducting the following steps:

1. Use the stasoft4 software to determine the required strong acid (H2SO4) dosage (prior

to introduction to the column), and the required strong base (NaOH) dosage to the
 mixed stream in order to reach the predefined water quality. Use the supplementary

material at the end of this lab protocol. Assume that the CCPP of the water leaving the

calcite reactor is -25 mg/l as CaCO3. The inner diameter of the column is 4.9 cm, a

bed-volume (BV) is defined as the total volume of reactor occupied by calcite. The

pumps are set to 80 ml/min.

The concentration of the H2SO4 is 1M

The concentration of NaOH is 0.02N

2. Dilute the acid with DIW to produce 4 liter of water with the required pH (i.e. at the

required acid dosage). Mix it well using a stirring rod. (step #1 in figure 1).

3. Place the feed pipe of the pump in the acidic solution tank (the 4 liter that you just

prepared) and fix it in place by using a clip.

4. The outlet pipe should be placed in the drainage.

5. Turn the pipe on. Make sure the flow rate is as required (use a stop watch and

cylinder)

6. Prepare a measuring cylinder with DIW (step #4 in the figure). Calculate the required

DIW and required volume of product water (effluents of the calcite column, #2 in the

figure) needed to reach the predefined %split, but DO NOT add this yet. The volume

of the mixture (DIW + product water from the column) should be 150 ml. Calculate

also the required volume of NaOH solution, step #3 in the figure (NaOH concentration

is 0.02 N). (Please calculate the volumes of solutions needed to mix in advance).

7. Let the process work until the BV is replaced 2 times. Meanwhile, analyze the tap

water, as described in section B. Afterwards, finish this experiment by conducting step

#7 - #9.

8. After at least 2 BV of inlet water were introduced to the column, place the outlet pipe

in the bottom of the measuring cylinder which already contains less than 150 ml of
 DIW. Raise the tube out of the water only at the end, to avoid mistakes in volume

measurement.

9. Add the base as far as possible from the water surface, and stir.

10. Now you have the stabilized water (#6 in the figure). Analyze the produced

mineralized water: measure pH, calcium and alkalinity, calculate the CCPP using

Stasoft.
Table 1: Required % split and water target for each couple of students

Group %split Calcium Alkalinity CCPP

number concentration
(mg/l as CaCO3) (mg/l as CaCO3) (mg/l as
CaCO3)
1 18 100 50 3<
2 18 100 50 4<
3 18 120 60 3<
4 18 120 60 4<
5 18 90 45 3<
6 20 100 50 4<
7 20 100 50 3<
8 20 120 60 4<
9 20 120 60 3<
10 20 90 45 4<
11 20 100 50 3<
12 25 100 50 4<
13 25 120 60 3<
14 25 120 60 4<
15 25 90 45 3<
16 25 100 50 4<
17 22 100 50 3<
18 22 120 60 4<
19 22 120 60 3<
20 22 90 45 3<
21 22 80 40 4<
22 22 80 40 3<
 B. Tap water characterization

TH analysis:

Blank analysis:

1. Fill a clean burette with EDTA solution (0.02N)

2. Measure 100 ml of DIW to a 150 ml beaker. Insert a stirring bar and place the beaker

on top of the magnetic stirrer.

3. Add 1 ml of the ammonia buffer solution and a few grains of the EBT indicator.

4. Titrate the EDTA solution until the color changes from purple to blue. One or two drops

of EDTA (if any at all) are usually enough for the DIW titration. The added volume is

denoted B [ml] in the equation below.

Tap water analysis:

1. Fill a clean burette with the EDTA solution (0.02N)

2. Measure 20 ml of tap water to a 150 ml beaker, dilute with approx. 80 ml of DIW. Insert

a stirring bar and place on top of the magnetic stirrer.

3. Add 1 ml of the ammonia buffer solution and a few grains of the EBT indicator.

4. Titrate the EDTA solution until the color changes from purple to blue. The added

volume is denoted as A [ml] in the equation.

TH calculation equation:

(A − B) ∙ N ∙ 50000 mg
= hardness in as CaCO
ml sample l

Where: A – EDTA solution volume needed to the sample titration (ml); B - EDTA solution

volume needed to the blank titration (ml); N – the EDTA solution concentration (eq/l); 50000

– equivalent weight of CaCO3 (mg/eq)

Determination of Ca2+ concentration in tap water

Blank analysis:

5. Fill a clean burette with the EDTA solution (0.02N)

6. Measure 100 ml of DIW to a 150 ml beaker. Insert a stirring bar and place the beaker

on top of the magnetic stirrer.

7. Add 3 ml of the NaOH solution (1 N) and a few grains of the HNB indicator.

8. Titrate the EDTA solution until the color changes from pink-purple to blue. One or two

drop are usually enough for the DIW titration (if any). The added volume is denoted B

[ml] in the equation.

Tap water analysis:

5. Fill a clean burette with the EDTA solution (0.02N)

6. Measure 20 ml of tap water to a 150 ml beaker, dilute with approx. 80 ml of DIW. Insert

a stirring bar and place on top of the magnetic stirrer.

7. Add 3 ml of the NaOH solution (1 N) and a few grain of the HNB indicator.

8. Titrate the EDTA solution until the color change from pink-purple to blue. The added

volume is denoted A [ml] in the equation.

Ca2+ concentration calculation equation:

(A − B) ∙ N ∙ 20000 mg
= Ca in
ml sample l
Where: A – EDTA solution volume needed to the sample titration (ml); B - EDTA solution

volume needed to the blank titration (ml); N – the EDTA solution concentration (eq/l); 20000

– equivalent weight of Ca2+ (mg/eq)

Lab report

1. Describe the methods and experiments performed.

2. Calculate the hardness of tap water.

3. Calculate Mg2+ and Ca2+ ions concentrations in tap water.

4. Calculate the pump flow rate in BV/hour, using the calcite volume in the reactor

used. Calculate how many BVs passed through the column before the effluents

were added to the DIW (i.e., before conducting step #7). Explain, why should

several BV of water flow through the column before mixing it with distilled

water?

5. Calculate the mass balance in the stabilization reactor. That is, calculate the

theoretical expected Ca, Alk (and pH, using stasoft) and compare it with the

measured results. Did you receive identical results as the software predicted? If

not, explain. What can be the reasons for these discrepancies? Based on the results,

try to conclude on each step in the experiment, and on each assumption.

Supplementary material – using the stasoft software

Simulating post treatment of desalinated water by dissolution of calcite using sulfuric acid.

Desalinated water must be stabilized (in this particular example) by dissolution of calcite in the

water using sulfuric acid, followed by addition of NaOH for pH adjustment. Assume that the

percent of treated water is 25%, water temperature is 25°C, TDS concentration upon exiting the

membrane is 30 mg/L and that the following water quality should be attained:

H2CO3*alk = 80 mg/L as CaCO3

3 mg/L as CaCO3 < CCPP < 10 mg/L as CaCO3

pH<8.5

That is, the water quality meets the Israeli regulation while ignoring the upper threshold for calcium

concentration.

For the purpose of design, assume that the water exiting the calcite reactor has a dissolution

potential of 25 mg/L as CaCO3 (i.e. CCPP = -25 mg/L as CaCO3). In other words, since the

water remains in the reactor for a limited amount of time, it does not reach equilibrium with the

solid phase.

What are the required dosages of chemicals and what will be the final quality of the water?

Solution

A screenshot of the Stasoft4 simulation is presented in Figure 2.

Carrying out the simulation: First identify the processes involved (H2SO4 and calcite dosage on

the first page; dilution and NaOH dosage on the second page). Next, calculate the required

dosage of CaCO3 (third column on the first page): Knowing that the approximate ratio of

alkalinity to calcium for this procedure is 2:1 and that alkalinity must be lower than 80 mg/L as
CaCO3 as well as that dilution downstream is 1 to 4, we can calculate that the amount of calcite

to be dissolved in the reactor is 640 mg/L:

mg Alkalinity as CaCO3 mg Ca as CaCO3

CaCO3 dosage  80 2
L product water mg Alkalinity as CaCO3
L treated water mg CaCO3
4  640
L product water L reated water

The required dosage of acid can be found by trial and error as follows: the acid dosage is

incrementally raised (second column on the first page) while monitoring the CCPP value; this

CCPP value is the value obtained after dissolution of the required concentration of calcite in

order to reach -25 mg/L as CaCO3. Note that the program characterizes qualities of water

resulting from dissolution of calcite beyond the dissolution potential of the water (i.e. the CCPP

value reaches positive values, despite the fact that this is practically illogical). The next step is

to define a dilution of 25% (this is to be done on a separate screen in the program). Lastly,

NaOH must be dosed such that the alkalinity rises to the required value (80 mg/L as CaCO3)

and so that the CCPP value is greater than 3.0 mg/L as CaCO3.

Observe that the simulation may be approached in different ways (through a different

combination of chemicals or dilution ratios) that will also guarantee arrival at the desired water

quality. An optimal solution to the problem will be one in which the cost of chemicals dosed

will be minimal. Accordingly, as chemical prices are always changing, the optimal solution is

not predetermined and therefore must be tested from time to time in order to find the cheapest

solution.
Figure 8-9
Simulation Results of Calcite Dissolution Using H2SO4 (First Page in the Program, Top

Screenshot); Dilution at a Ratio of 1:4 and NaOH Addition for pH Adjustment (Second

Page, Bottom Screenshot)

Figure 2

Simulation Results of Calcite Dissolution Using H2SO4 (First Page in the Program, Top

Screenshot); Dilution at a Ratio of 1:4 and NaOH Addition for pH Adjustment (Second

Page, Bottom Screenshot)