HARDNESS REMOVAL: Lime – Soda Ash Softening Process

Hardness
• The term is used to characterize a water that does not lather well, causes a scum in the bath tub, and leaves white,
hard, crusty deposits (scale) on coffee pots, tea kettles and hot water heaters
• The failure to lather well and the formation of scum on bath tubs is the result of the reaction of calcium and
magnesium with the soap.
Example: Ca2+ + (soap) → Ca(soap)2 ↓
• As a result of this complexation reaction, soap cannot interact with the dirt on clothing, and the calcium-soap complex
itself forms undesirable precipitates.
• The hardness is usually measured as the total calcium and magnesium concentration in mg/L or meq/L as calcium
carbonate, CaCO3. This is called the “total hardness.”

HARD WATER CLASSIFICATION

Hardness (mg/L CaCO3) Description
0 – 50 Extremely soft
50 – 100 Very soft
100 – 150 Soft to Moderately hard
150 – 300 Hard
>300 Very Hard

Water Hardness in Nature

• Hardness in natural waters comes from the dissolution of minerals from geologic formations that contain calcium and
magnesium.
• Two common minerals are calcite (CaCO3) and dolomite [CaMg(CO3)]2.
• As rainwater enters the topsoil, the respiration of microorganisms increases the CO2 content of the water.
CO2 + H2O → H2CO3
CaCO3 and CaMg(CO3)]2 + H2CO3 →[Ca(HCO3)2] and [Mg(HCO3)2] soluble in water
CaCl2, CaSO4, MgCl2, and MgSO4 may also go into the solution to contribute to the hardness.
• In the neutral pH range and at ambient temperatures, a concentration greater than 100 mg/L as calcium carbonate is
considered hard
• Lime/soda-ash precipitation of water hardness is theoretically capable of reducing hardness to about 25 mg/L, but only to
50–80 mg/L in practical terms; this is usually adequate for domestic and many industrial uses

TOTAL HARDNESS
The calcium and magnesium ions predominate and the convention in performing softening calculations is to define the total
hardness (TH) of water as a sum of these elements in mg/L as CaCO3 or meq/L
TH = Ca2+ + Mg2+
TH = CH + NCH
Two components of total hardness are:
1. That associated with HCO3- anion (carbonate hardness, CH)
2. That associated with other anions (non-carbonate hardness, NCH).

Carbonate Hardness
 The portion of the hardness with an equivalent carbonate concentration is termed “temporary hardness” because
boiling water removes it and increases the pH or carbonate hardness (CH), because the complementary ion for the
precipitation of the calcium is already present.
 Operationally, this is measured as the total hardness minus the alkalinity, because in the neutral pH range the
alkalinity mostly consists of bicarbonate ions expressed as equivalents of calcium carbonate.

Non-carbonate Hardness
 The remaining hardness is called “permanent hardness” hardness because it is not removed by heating; it is also the
total hardness in excess of the alkalinity and is associated with other anions or non-carbonate hardness (NCH).
 In order to complete the treatment, some form of carbonate must be added in the form of soda ash; this reaction
removes the calcium non-carbonate hardness (CaNCH), which is equal to the equivalents of calcium minus the
equivalents of carbonate species
 Magnesium non-carbonate hardness (MgNCH) can also be defined as equal to the equivalents of magnesium
present if there are fewer equivalents of carbonate species than of calcium, or,
ChE 513: Industrial Waste Management and Control
Engr. MMM Boado, MSEnE
  the MgNCH is equal to the total NCH if the carbonates exceed calcium equivalents
 If there is magnesium non-carbonate hardness, soda ash must be added to precipitate the calcium from the lime used

SOFTENING
 In lime/soda-ash softening, it is necessary to add slaked lime, Ca(OH)2, or CaO to raise the pH, converting the free CO2,
carbonic acid and bicarbonate forms of dissolved carbon dioxide to carbonate ions
 At pH greater than 10.8, the calcium will then precipitate as calcium carbonate, and magnesium as its hydroxide

When alkalinity < total hardness, Carbonate hardness = alkalinity (in consistent units)

When alkalinity > total hardness, Carbonate hardness = total hardness (in consistent units)

Sample Problems
1. A water has an alkalinity of 200 mg/L as CaCO3. the Ca2+ concentration is 160 mg/L as the ion, and the Mg2+
concentration is 40 mg/L as the ion. The pH is 8.1. Find the total, carbonate and noncarbonate hardness.
2. Given the following analysis of a groundwater, construct a bar chart of the constituents, expressed as CaCO 3

ChE 513: Industrial Waste Management and Control

Engr. MMM Boado, MSEnE
Relationship of pH and alkalinity
pH simply expresses the degree of hydrogen ion concentration. Alkaline means that the pH is greater than 7. Alkalinity is the
true measure of acid-neutralizing capacity which includes the bicarbonate (HCO3-), carbonate (CO3-2) and hydroxide (OH-)
ions. It is measured in mg/L as CaCO3 or meq/L.

 At a pH of approximately 4.3 and below, we see there is no alkalinity present. There is only free mineral acidity (FMA)
and dissolved carbon dioxide.
 As we increase the pH, the dissolved carbon dioxide starts to convert to bicarbonate ion between 4.3 and 8.3. This
conversion is complete at a pH of about 8.3, where only bicarbonate is present.
 Increasing the pH beyond 8.3, the bicarbonate ion is converted to carbonate ion. Conversion is nearly complete at a pH
around 10.2 with almost all the bicarbonate being converted to carbonate.
 Further increasing the pH past 10.2, we start seeing measurable levels of hydroxide ions along with the carbonate
ions.
 If the lime/soda ash process is used to soften the water, re-carbonation may well be needed

STEP – WISE REACTIONS

a. Any free acids are neutralized
b. The pH is raised to precipitate CaCO3
c. If necessary, the pH is raised further to remove Mg(OH) 2
d. If necessary CO3- is added to precipitate the NCH

1. Neutralization of carbonic acid

CO2 + Ca(OH)2 ↔ CaCO3 + H2O
 to raise pH, free acids must be neutralized first; CO2 is usually expressed as H2CO3
 No hardness is removed

2. Precipitation of carbonate hardness due to calcium

Ca2+ + 2HCO3- + Ca(OH)2 ↔ 2CaCO3 + 2H2O
 to precipitate calcium carbonate, all of the naturally occurring bicarbonates must be converted

3. The carbonate then serves as the common ion for the precipitation reaction.

4. Precipitation of carbonate hardness due to magnesium

To remove MgCH, more lime is added and proceeds in 2 stages
a) Bicarbonate converts to carbonate
Mg2+ + 2HCO3- + Ca(OH)2 → 2CaCO3 + MgCO3 + 2H2O

b) MgCO3 is soluble (hardness does not change), add more lime to remove hardness due to magnesium
Mg2+ + CO32+ + Ca(OH)2 → Mg(OH)2 + CaCO3

5. Removal of non-carbonate hardness due to calcium

Ca2+ + Na2CO3 → CaCO3 + 2Na+ Additional carbonate is added in the form of soda ash

6. Removal of non-carbonate hardness due to magnesium

Mg2+ + Ca(OH)2 → Mg(OH)2 + CaCO3 + 2Na+ Ca2+ + Na2CO3 → CaCO3 + 2Na+
 The lime provides the hydroxyl ion for precipitation of the magnesium
 Ca2+ is still in solution, so soda ash is added in combination
ChE 513: Industrial Waste Management and Control
Engr. MMM Boado, MSEnE
Removal of CO2
 Because CO2 in the raw water behaves as H2CO3, its removal is the first step in raising the pH in lime-soda softening.
 It may be neutralized by the addition of lime, in which case it is not a “process” in the conventional meaning of the
word.
 When the concentration exceeds 10 mg/L as CO2 (227 mg/L as CaCO3 or 0.45 meq/L), the economics of removal by
aeration (stripping) are favored over removal by lime neutralization.
 Air stripping is a separate process.
 No hardness is removed in this process.

Lime Softening
 It is also called selective calcium removal or partial lime softening.
 Only lime is added.
 The desired control pH is 10.3.
 This process removes only carbonate hardness caused by calcium.

Excess lime softening

 Only lime is added.
 The desired controlled pH is 11.3.
 This process removes only the carbonate hardness caused by calcium and magnesium.

Lime-soda softening
 Both lime and soda ash are added.
 The desired control pH is 11.3.
 The process removes both carbonate and non-carbonate hardness caused by calcium and magnesium.

PROCESS LIMITATIONS AND EMPIRICAL CONSIDERATIONS

 Lime-soda softening cannot produce a water completely free of hardness because of the solubility of CaC0 3 and
Mg(OH)2, the physical limitations of mixing and contact, and the lack of sufficient time for the reactions to go to
completion.
 Thus, the minimum calcium hardness that can be achieved is about 30 mg/L as CaC0 3 and the minimum magnesium
hardness is about 10 mg/L CaC03.
 In recent years, many utilities have raised the target hardness to 120 to 150 mg/L as CaC0 3 to reduce chemical cost
and residuals production (Horsley et al., 2005)
 Based on empirical experience, the minimum extra amount is 20 mg/L of Ca(OH) 2 expressed as CaC03
 Because of the expense of removing magnesium, normally only the magnesium in excess of 40 mg/L as CaC0 3 is
removed as these form scales on heat exchangers
 Addition of extra lime in amounts greater than 40 mg/L mg/L as CaC0 3 does not appreciably improve the addition
kinetics.
 Because excess lime adds hardness in the form of Ca2+, it is removed in a subsequent re-carbonation process
 One process to achieve a specified magnesium concentration or to achieve a given hardness is to treat a portion of
water to the practical limits and then blend the treated water with the raw water to achieve the desired concentration
or hardness.
 Stoichiometric amounts of lime and soda are added to remove all the Ca 2+ and Mg2+ to the practical limits of softening
(that is, 0.60 meq/L or 30 mg/L as CaCO3 of Ca2+ and 0.20 meq/L or 10 mg/L as CaO3 of Mg2+

CHEMICAL DOSAGES
Lime and Soda Ash Equivalent Dosages
Equivalents of
Constituent to be removed
Lime Soda Ash
H2CO3 1 0
Calcium carbonate hardness CaCH 1 0
Magnesium carbonate hardness MgCH 2 0
CaNCH 0 1
MgNCH 1 1

The stoichiometric approach assumes the reactions go to completion and thus may overestimate the required dosage. This is
not a real problem, because in practice it is necessary to increase the dosage by 5–10% above the stoichiometric amount
in order to ensure rapid formation of precipitate.
ChE 513: Industrial Waste Management and Control
Engr. MMM Boado, MSEnE
ESTIMATING CO2 CONCENTRATION
 The approximate concentration of CO2 may be estimated using the equilibrium expressions for the dissociation of
water and carbonic acid with the definition of alkalinity
 The pH and alkalinity of the water must be determined to make the estimate
 The equilibrium expressions for carbonic acid are:

 For water temperatures other than 25oC, the dissociation constants may be estimated as

where T absolute temperature, K.

 When the pH is less than 8.3, HCO3 is the dominant form of alkalinity, and total alkalinity is nominally taken to be
equal to the concentration of HCO3 thus, we can ignore the dissociation of bicarbonate to form carbonate

a. Calculate the [H+] from the pH.

b. Correct the Ka value for temperature.
c. Calculate the [HCO3-] from the alkalinity.
d. Solve the first equilibrium expression of the carbonic acid dissociation for [H2CO3].
e. Use the assumption that [CO2]=[H2CO3] to estimate the CO2 concentration.

RECARBONATION
 The process is accomplished by bubbling (diffusion) gases containing CO2 through water; this aims to replace the
carbon dioxide gas removed by the addition of lime
 Re-carbonation is often necessary to prevent after precipitation on the filters or in the distribution piping because
the retention time in settling basins is usually inadequate to permit complete formation of the insoluble compounds
 Carbonates in solution may run out if part of the hardness is due to permanent hardness
 The insoluble precipitates sought are calcium carbonate, CaCO3, and magnesium hydroxide, Mg(OH)2 with solubility
products as follows:

𝐶𝑎𝐶𝑂3 𝐾𝑠𝑝 = [𝐶𝑎2+ ][𝐶𝑂3 2− ] = 5𝑥10−9
𝑀𝑔(𝑂𝐻)2 𝐾𝑠𝑝 = [𝑀𝑔2+ ][𝑂𝐻 − ]2 = 9𝑥10−12

CO2 + Ca2+ + 2OH- ↔ CaCO3 + H2O CO2 + Mg(OH)2 ↔ Mg2+ + CO32- + H2O
CO2 + CaCO3 + H2O ↔ Ca2+ + 2HCO3- CO2 + Mg2+ + CO32- + H2O ↔ Mg2+ + 2HCO3-

PROBLEM (recall of Ksp)

25.0 mL of 0.0020M potassium chromate are mixed with 75.0 mL of 0.000125M lead(II) nitrate. Will a precipitate of lead(II)
chromate form? Ksp of lead(II) chromate is 1.8 x 10-14.

ChE 513: Industrial Waste Management and Control

Engr. MMM Boado, MSEnE