EXERCICE : Carbonate equilibrium

Drinking water is produced in a water production plant. The produced discharge is Qproduced = 1000
m3/h. Following the step of clarification, water needs to be at the equilibrium before being sent into
the distribution network.

The water chemical characteristics are the following :

Ca2+= 60 mg/l Na+=23 mg/l HCO3-=152,5 mg/l SO42-= 72 mg/l pH=6,6 T°=10°C

Molar Masses : Ca2+= 40 g/moles Na+=23 g/moles HCO3-=61 g/moles SO42-= 96 g/moles

1- Draw the diagram which gives the water composition for the cation and anion in °F
2- Give the value of the total hardness (TH) , alkalinity (TAC), permanent and temporary
hardness
3- Draw the equilibrium line on the Hallopeau and Dubin diagem. Is this water agressive or scale
forming ????
4- One wants to distribute this water at the equilibrium pH through a treatment using lime
(CaOH2). With the help of the Hallopeau and Dubin diagram,
4.1- Gives the final composition of the water (TH, TAC, pH)
4.2- Check your results by calculating the value of pHs and pH with the theoretical formula.
Comment the results

5-

5.1- What is the quantity of lime necessary to treat 1l of water ?

5.2- On a practical point of view, the lime is stored as a concentrated solution with a
concentration C0= 2 g/l. This solution is injected in a mixing tank (where the reaction will
take place) before sending the water to distribution (after a desinfection stage of course).
- Gives the lime injection flowrate as well as the volume of the storage reservoir in order
to get an autonomy equal to one day
- Given the size of the storage tank, make your comment….

Solution

1- There are many ways to calculate the concentration in °F. If you are familiar with the ionic
units, you can make directly the calculation from the equivalent mass of each ions.

For instance for Ca2+, [Ca2+]meq/l= 60/(40/2)=3 meq/l so [Ca2+]=3x5=15°F

If you prefer, you can make the calculation using the concentration in mmol/l as an
intermediate calculation.
Then you can use the relationship 1 meql/l of any specie = 1/n mmol/l of that specie (with n
the absolute value of the valence)

For exemple for Ca2+

 The mass concentration Ca2+ = 60 mg/l correspond to a molar concentration
[Ca2+]mmol/l=60/40=1,5 mmol/l

As the valence n is 2 for Ca2+, for that specie, 1 meq/l=0.5 mmol/l so [Ca2+]meq/l=2x1,5 = 3
meq/l = 15°F

All calculation made we get : [Ca2+]=15°F [Na+]=5°F [HCO3-]=12,5°F and [SO42-]=7.5°F. The
diagram below reprents this water in terms of cation and anion. The electrical charges balance
is fullfilled.

0 15°F 20°F
Ca2+ Na+
HCO3- SO42-
0 12.5°F 20°F

2- From the diagram above :

TH=15°F and TAC=12.5°F
Temporary hardness = TAC (as TAC<TH) = 12.5°F
Permanent hardness = TH-TAC (in that case as TAC<TH) = 2.5°F

3- Calculate the ratio TAC/Ca2+ (using °F or meq/l as unit). Here TAC/Ca2+=0,83

Knowing the temperature you can place a point in the little diagram on the top left of the
Hallopeau & Dubin diagram. The equilibrium line go through this point and is parallel to the
equilibrium line already shown on the diagram.

The representative point for the raw water is given by the coordinate (TAC, pH). There are two
scales for the abscissa. As the grid on the diagram correspond to the second scale (mg/l
equivalent CaO), i made a correspondance between the two scales in order to be more precise.

Here the TAC value is 12,5°F that is to say 125 mg/l equivalent CaCO3 (first scale). On the
diagram, we see that the value 90 on the CaCO3 scale correspond exactly to 50 on the CaO
scale. So 125 mg/l equivalent CaCO3 = 69,4 ~ 70 mg/l equivalent CaO wich makes the
representative point easier to represent on the diagram.

This point is under the equilibrium line so the water is agressive :

4-
Translate the curve corresponding to the lime (or related) products (« Neutralisation par la
chaux), till it goes through the water representative point.

4.1 I found pHfinal =7.6 and TACfinal =180 mg/l equivalent CaCO3=18°F.

The chemical reaction involved is : CaOH2 + CO2 + H2O → Ca(HCO3)2

So expressed in °F (or meq/l) the hardness increase is the same as the TAC increase (as the
reaction between lime and free CO2 gives one mole of Ca2+ dissolved for 2moles of HCO3-
produced)
So THfinal=THinitial + (TACfinal-TACinitial) = 15+ (18-12,5)=20,5°F. As there si no Mg2+ in the water,
the value of TH is also the value of the Ca2+ concentration

4.2 We can use the two formula for pH and pHs. We should find the same value as the water
is at the equilibrium.

𝑙𝑜𝑔10[𝐶𝑂2 𝑎𝑞 ] = 𝑙𝑜𝑔10[𝑇𝐴𝐶] − 𝑝𝐻 + 𝑙𝑜𝑔10(𝑝) + 𝑝𝐾1′ (eq1)

𝑝𝐻𝑠 = 𝑝𝐾2′ − −𝑙𝑜𝑔10[𝐶𝑎2+ ] − 𝑝𝐾𝑠′ − 𝑙𝑜𝑔10[𝑇𝐴𝐶] + 𝑙𝑜𝑔10(𝑝) (eq2)

First one must calculate the pKi knowing the temperature (Cf slide). I found :

pK1 = 6,476, pK2 = 10,49 , pKS = 8,15

The pKi’ value are corrected using the ionic strength, so the pKi’ evolves as the treatment
progress.

- here, if we suppose that the ionic strenght is only due to the species given in the text,
knowing the final state for the water composition is sufficient (knowing that the Na+
and SO42- concentration does not evolve)
- the ionic strength that is calculated from the procedure above can be slightly different
from the one used in the diagram. Indeed, the diagram is drawn for fixed value of pKi’
considering an average temperature (15°C) and an average composition corresponding
to dry residues equal to 200 mg/l. There is a correspondance between the ionic
strength and the dry residue which is often taken as a proportional relationship.
I have taken the relation : µ (mol/l) =25 10-6 x Dry residu (mg/l) that is often found in
literature (but depending on the source you can find slightly different coefficient)

With the first method :

µ=1/2 x{ [Ca2+] + [HCO3-] + [Na+] + [Cl-]} = 1/2 { [THfinal] + [TACfinal] + [Na+] + [Cl-] =0,0037 mol/l

With the second methods : =25x10-6 x 200 = 0,005 mol/l

So the discrepency due to the use of the « real » ionic strength or the average one should
not be too different.

The correction for the pKi’ is given by :

pK1 ' = pK1 − 
pK 2 ' = pK 2 − 2
pK s ' = pK s −  s
ou pK s' = pK s − 4
pK e ' = pK e − 

With
  =  (1 + 1,4  )
 S = 4  (1 + 3,9 )
Using the  and s and the « real » ionic strenght value, i found :

pK1’=6,42 , pK2’=10,377 , pKs’=7,916

Using eq1 (with the concentration in mol/l and neglecting log10(p) ), i found pH=7,66
The CO2 concentration is read on the diagram (9 mg/l)

Using eq2, i found pH=7,593

The values are very similar to the one found with the diagram (knowing that the results can be
sensitive to the reading of the CO2 concentration). Beware, for a departure of the real T° from
15°C (the temperature used for the pKi’ calculation in the Hallopeau & Dubin diagram), the
discrepancy would be probably higher.

Remark : 𝑝 = 1 + 2𝐾2′ ⁄[𝐻 + ] with [H+] = 10-pH and K2’=10-PK2’

So with pH=7,6 and pK2’=10,377, p=1,0033 and log10(p)=0,0014. So this term can be neglected

5- The increase in [Ca2+] comes directly from the addition of lime (cf the chemical reaction above).
So the [Ca2+] concentration (present in the lime) which is consumed is equal to :

[Ca2+] in lime consumed= [Ca2+]final – [Ca2+]initial= [ THfinal- THinitial] = TAC=5,5°F

[Ca2+] in lime consumed = (5,5/5)/2 = 0,55 mmol/l

There is one mole of Ca2+ in one mole of lime CaOH2 so the lime consumed is 0,55 mol/l
(meaning 0,55 moles per liter of water treated)

As the molar mass of the lime is 40+17x2 = 74 g/mol , the amount of lime required is
0,55*74=40,7 mg/l

Remark : as this 40,7 mg/l correspond to a total increase of TAC equal to 5,5°F, it corresponds
indeed to the data state on my slide : 7,4 mg/l of lime is required for each °F of TAC

The end of the question is similar to the practical made on Coagulation-Floculation.

The lime mass-flowrare required is : 𝑚̇ = 𝑄 × 𝐶𝑙𝑖𝑚𝑒_𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑 = 1000 × 0,0407 = 40,7 𝑘𝑔/ℎ

The lime injection rate (from the storage tank) is : 𝑄𝑙𝑖𝑚𝑒 = 𝑚̇⁄𝐶0 = 20,35 𝑚3 /ℎ

The storage volume is V=488 m3 which is rather big (knowing that the tank should be refilled
every day). C0 can not be increased as 2 g/l correspond to the maximum solubility of lime in
water.

Here a treatment through a complete degasing of the excess CO2 could be better (or a
combination of degasing + lime injection in order to reduce the amount of the lime required