9-Softning_F12

Water Softening (Precipitation Softening) (3rd DC 178; 4th DC 235)

1. Introduction
Hardness
- Multivalent metal ions which will form precipitates with soaps.
e.g.
Ca2+ + (soap)

Ca(soap)2 (s)

Complexation reaction
2+
a. Caused by ions of Ca2+ and Mg
2+

- Hardness in water is caused by ions of Ca and Mg2+

b. Other hardness constituents: Iron (Fe), manganese (Mn), strontium (Sr), aluminum
(Al).
- Iron (Fe), manganese (Mn), strontium (Sr), aluminum (Al) also produce hardness.

c. Sources - Largely the result of geological formations of the water source.

:

Precipitation
::
:

------------------------------------------------------------------/// /// Top organic soil - microbial activity /// ///

CH2O
+ O2 CO2 + H2O
organics
-----------------------------------------------------------------Subsoil
CO2 + H2O
H2CO3
-----------------------------------------------------------------Limestone formation weathering
CaCO3(s) + H2CO3
MgCO3(s) + H2CO3

CaCO3(s) + H+(aq)

HCO3-(aq) + Ca2+(aq)

Ca(HCO3)2
Mg(HCO3)2

60C

15C

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Types of Hardness

with respect to cations (metallic ion)

with respect to anions (nonmetallic ion)

1) With respect to cations (metallic ion; Ca2+, Mg2+)

a. Calcium Hardness:
b. Magnesium Hardness:

Ca(HCO3)2, CaSO4, CaCl2

Mg(HCO3)2, MgSO4, MgCl2

Total Hardness (TH) = Calcium Hardness + Magnesium Hardness

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2) With respect to anions (nonmetallic ion; HCO3 , SO42-, Cl )

a. Carbonate Hardness (CH)

b. Noncarbonate hardness (NCH)
Carbonate Hardness (Temporary Hardness)
- heating the water removes it.
Calcium bicarbonate
Magnesium bicarbonate

Ca(HCO3)2
Mg(HCO3)2

Carbonate hardness = alkalinity, when alkalinity < TH

Carbonate hardness = TH, when alkalinity > TH
where TH = total hardness
* Alkalinity - measured as the amount of acid required to titrate to PH 4.3.

(e.g., HO-, CO 3 2- , HCO 3 -)

Noncarbonate hardness (Permanent hardness)

- not removed when water is heated
- will not precipitate when the water is boiled
Calcium sulfates
Magnesium sulfates
Calcium chlorides
Magnesium chlorides

CaSO4
MgSO4
CaCl2
MgCl2

Total Hardness (TH) = Carbonate Hardness (CH) + Noncarbonate hardness (NCH)

d. Expressed in mg/L as CaCO3

- The sum of calcium and magnesium concentrations expressed in mg/L as CaCO 3.

eq. wt of CaCO3
Hardness (mg/L as CaCO3) = (mg/L of M ) -----------------------eq. wt of M2+
2+

Hardness (mg/L as CaCO3)

= (meq/L Ca2+ + meq/L Mg2+) (ew. wt of CaCO3)
(eq. wt of CaCO3 = 50 mg/meq)
Note: EW = equivalent weight, mg/meq
meq mg
mg
------ -------- = -----L
meq
L
2+

CaCO3 Ca

+ CO3

2-

CO3

2-

2H

H2CO3

(z = 2)

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Example: Given Ca2+ = 70 mg/L and Mg2+ = 9.7 mg/L

Determine calcium hardness, magnesium hardness, and total hardness as CaCO3.
(Solutions)
EW of Ca2+ = 20 mg/meq
EW of Mg2+ =12.2 mg/meq
EW of CaCO3 = 50 mg/meq
50 mg/meq CaCO3
Calcium hardness = (70 mg/L Ca ) --------------------------20 mg/meq Ca2+
2+

= 175 mg/L hardness as CaCO3

50 mg/meq CaCO3
Magnesium hardness = (9.7 mg/L Mg2+) --------------------------12.2 mg/meq Mg2+
= 40 mg/L hardness as CaCO3
Total hardness = (175 + 40) = 215 mg/L as CaCO3

Example:

Given Ca2+ = 3.5 meq/L and Mg2+ = 0.795 meq/L.

Determine total hardness as CaCO3.

(Solution)
Total hardness = (3.5 meq/L + 0.795 meq/L) (50 mg/meq CaCO3)
= 215 mg/L as CaCO3

Hard Water Classification Table 3-13 (DC 179); Table 4-14 (4th DC 236)

Hardness Range
Description
mg/L as CaCO3
-------------------------------------------------------------0 - 75
Soft
75 -100
Moderately hard
100 - 300
Hard
>300
Very Hard
--------------------------------------------------------------

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Hardness >300 mg/L as CaCO3 is considered excessive for public water supply
- results in
a. high soap consumption
b. scale in heating vessels and pipes
Mg2+ in excess of ~40 mg/L as CaCO3 forms scale on heat exchange elements in hot water
heaters

Goal of water treatment (softening) is 75120 mg/L as CaCO3

(3rd DC, 179)

From other literature

-------------------------------------------------------------------------------------------a. High (excessive) hardness
>300 mg/L as CaCO3
b. Hard

150 - 300 mg/L as CaCO3

(100 - 300 mg/L as CaCO3)

c. Moderate hardness

60-120 mg/L as CaCO3

(75 -150 mg/L as CaCO3)
- is considered moderately hard

d. Soft

0 - 75 mg/L as CaCO3

e. Acceptable

80-100 mg/L as CaCO3

- acceptable for a public water supply

- but magnesium content should not exceed 40 mg/L as CaCO3
--------------------------------------------------------------------------------------------

2. Chemistry of Water Softening

Lime-soda ash processes
a. The lime-soda ash water-softening process uses:
Lime, Ca(OH) 2 (or CaO) and Soda ash, Na2CO3
to precipitate hardness as:
Calcium carbonate, CaCO3(s)
Magnesium hydroxide, Mg(OH)2(s)
b. Chemical reactions:
a. CO2
- is not hardness but it consumes lime and must therefore be considered in calculating the amount required.

CO2 + Ca(OH)2 CaCO 3(s) + H2O

(1)

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b. Carbonate hardness
- is precipitated by lime.

Ca(HCO3)2 + Ca (OH)2 2CaCO3 (s) + 2H2O

(2)

Mg(HCO3)2 + Ca(OH)2 CaCO3 (s)

(3)

MgCO3

+ MgCO3 + 2H2O

+ Ca(OH)2 Mg (OH)2 (s) + CaCO 3 (s)

(4)

Note:
- 1 mole of lime is needed for each mole of calcium bicarbonate (Rxn 2)
- 2 moles of lime are required for each mole of magnesium bicarbonate (Rxns 3 and 4).

c. Noncarbonate hardness
- requires the addition of soda ash for precipitation
MgSO 4 + Ca(OH) 2 Mg(OH) 2(s) + CaSO4

(5)

CaSO4 + Na2CO3 CaCO 3(s)

+ Na2SO4

(6)

MgCl2 + Ca(OH) 2 Mg(OH) 2(s)

+ CaCl2

(7)

CaCl2 + Na2CO3 CaCO 3(s)

+ 2 NaCl

(8)

Note:
- 1 mole of lime Ca(OH)2 and 1 mole of soda ash Na2CO3 are needed to each mole of
MgSO4 or MgCl 2
- 1 mole of soda ash Na2CO3 is needed to each mole of CaSO4 or CaCl 2
Solubility of CaCO3(s) and Mg(OH)2(s)
- Precipitation softening cannot produce water completely free of hardness because of:
a. Solubility of CaCO3(s) and Mg(OH)2 (s)
= (0.6 meq/L of CaCO3) + (0.2 meq/L of Mg(OH)2)
= (30 mg/L CaCO3) + (10 mg/L of Mg(OH) 2 as CaCO3)
Total limiting hardness = 40 mg/L as CaCO3

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- The minimum practical limits of precipitation softening = 30 mg/L of CaCO 3 and10

mg/L of Mg(OH)2 expressed as CaCO3
Goal is 75 120 mg/L hardness as CaCO3
Deviations from the theoretical hardness removal by the lime-soda ash treatment.
- Limited completion of the chemical reactions by physical considerations;
e.g., inadequate mixing, limited detention time in settling basins

Advantages of Lime-Soda ash Softening

a. Hardness is taken out of solution
b. Lime added is also removed.
+
-

when soda ash is applied, Na remains in the finished water.

noncarbonate hardness requiring soda ash is generally a small portion of the total hardness.

c. TDS (total dissolved solids) is reduced

- Lime also precipitates the soluble Fe and Mn
- TDS may be significantly reduced.
d. Disinfection
- Excess lime treatment provides disinfection
e. Aids in coagulation
- Excess lime treatment provides aids in coagulation for removal of turbidity

Schemes of lime-soda ash softening

- three different basic schemes may be used to provide a finished water with the desired
hardness.
a. Excess lime treatment
b. Selective calcium removal
c. Split treatment

9-Softning_F12

Excess Lime Treatment

1) Carbonate hardness associated with Ca2+ can be effectively removed to the practical
limit of CaCO3 solubility (30 mg/L) by stoichiometric additions of lime.
Ca(HCO3)2 + Ca(OH)2 2CaCO3(s) + 2H2O
2) Precipitation of Mg2+ calls for a surplus of approximately 1.25 meq/L (30 mg/L) of
CaO above stoichiometric requirements.
3) The practice of excess-lime treatment reduces the total hardness to about 40 mg/L
as CaCO3
i.e., 30 mg/L of CaCO3 as CaCO3
10 mg/L of Mg(OH)2 as CaCO3
4) After excess-lime treatment, the water is scale forming and must be neutralized to
remove caustic alkalinity (OH-).
- Recarbonation and soda ash are regularly used to stabilize the water
5) CO2 neutralizes excess lime as follows:
Ca(OH) 2
+
excess lime

CO2 CaCO3(s) +

H2O

- this reaction precipitates calcium hardness and reduces the pH from near 11 to about 10.2.

6) Further recarbonation of the clarified water converts a portion (say 1/2) of the
remaining carbonate ions to bicarbonate by the reaction.
CaCO 3(s) + CO 2 + H2O

Ca(HCO3) 2

- the final pH is in the range 9.5 to 8.5, depending on the desired carbonate to bicarbonate ratio.

9-Softning_F12

Bar Diagram (Bar Graph)

- purpose is to visualization of the chemical composition
- data may be expressed in meq/L (milliequivalents per liter).
a) Top row of the bar graph consists of major cations arranged in the order of Ca 2+, Mg2+,
Na+, K+.
b) Bottom row of the aligned in the sequence of OH, CO32, HCO3 , SO42, Cl-, NO3-.
c) The sum of the positive meq/L must equal the sum of the negative meq/L for a given
water sample in equilibrium.
Ion Balance or
I Cations - Anions l
Charge Balance = ---------------------------------- x 100
Cations + Anions
< 5%

OK

Example: WATER SOFTENING - Excess Lime Treatment

The water defined by the analysis given below is to be softened by excess lime treatment
in a two-stage system.
Given chemical Analysis Data: CO2 = 8.8 mg/L; Ca 2+ =70.0 mg/L; Mg2+ = 9.7 mg/L; Na+ =
6.9 mg/L; HCO3 =115.0 mg/L as CaCO3; SO42- = 96.0 mg/L; Cl = 10.6 mg/L
1. Sketch a bar graph for:
a) the raw water,
b) softened water after chemical addition and settling, but before recarbonation and
filtration,
c) softened water after 1st stage recarbonation,
d) softened water after 2nd stage recarbonation and filtration assuming that one-half of
the alkalinity is in the bicarbonate form.
2. List the hypothetical combinations of chemical compounds in the raw water.
3. Calculate the quantity of softening chemicals required in lb/MG of water.
4. Calculate the theoretical quantity of CO2 needed to provide finished water with of
the alkalinity converted to bicarbonate ion.

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(SOLUTIONS)
1. Express the concentrations in meq/L
a. Sketch a meq/L bar graph for the raw water.
b.
Species
Conc.
MW
z
MW/z = eq.wt
(mg/L)
(g/mol)
(mg/meq)

mg/L
------------ = meq/L
mg/meq

Total
(meq/L)
0.4

CO2

8.8

44

22.0

0.4

Cations
Ca 2+

70.0

40.1

20.0

3.5

Mg2+

9.7

24.3

12.2

0.795

6.9

23.0

23.0

0.3

115

100

50.0

2.3

96.0

96.0

48.0

2.0

10.6

35.5

35.3

0.3

Na

Anions
HCO3
(as Ca CO3)
SO4 2

Cl

4.595

4.6

b. Check ion balance

Ion Balance or
I Cations - Anions l
Charge Balance = --------------------------------- x 100
Cations + Anions
I 4.595 - 4.6 l
= ----------------------- x 100 = 0.05 % < 5%
4.595 + 4.6

Ion Balance is OK

2. Sketch a bar graph for the raw water. - See the bar graph below: 1) Raw water
3. Calculate the softening chemicals required.
1) List the combination and concentration (meq/L) of chemical compounds from the
bar graph (Raw water)
Compound

(meq/L)

CO2

0.4

Ca(HCO3)2

2.3

CaSO4

1.2

MgSO 4

0.8

NaCl

0.3

10

9-Softning_F12

Lime Required
CO2:

CO2
0.4

Ca(OH)2 CaCO 3(s) + H2O

0.4

(1)

Ca(HCO3)2: Ca(HCO3)2 + Ca (OH)2 2CaCO3 (s) + 2H2O (2)

2.3
2.3
MgSO 4 + Ca(OH) 2 Mg(OH) 2(s) + CaSO4 (5)
0.8
0.8
0.8
---------------------------------------------------------------------------------------(meq/L)
3.5
3.5
MgSO 4:

Soda Ash Required

CaSO4:
CaSO4 + Na2CO3 CaCO 3(s) + Na2SO4 (6)
Raw water
1.2
1.2
Produced w/Lime
0.8
0.8
_____________________________________________________
(meq/L)
2.0
2.0

Calculate eq.wt of lime and soda ash

MW
Quick Lime

CaO

Soda Ash

Na2CO3

z eq.wt (mg/meq)

56.1 2

28.0

106

53.0

Lime (as CaO) required = stoichiometric requirement + excess lime

= (3.5 meq/L)(28 mg/meq) + (1.25 meq/L)(28 mg/meq)
= 133 mg/L CaO
= (133 mg/L)(8.34 lb/MG per mg/L) = 1100 lb/MG
Soda ash required = (2.0 meq/L)(53 mg/meq)
= 106 mg/L Na2CO3
= (106 mg/L)(8.34 lb/MG per mg/L) = 884 lb/MG

11

9-Softning_F12

(c) Sketch an meq/L bar graph for the water after lime and soda ash additions and settling,
but before recarbonation
1) Calculate solubilities (in meq/L)
mg/L eq.wt (mg/meq) meq/L
CaCO3 as Ca CO3
Mg(OH)2 as Ca CO3

30
10

50
50

0.6
0.2

After the addition of softening chemicals

CATIONS

(meq/L)

2+

Excess lime, Ca(OH)2

1.25

2+

Ca
Mg2+

Solubility of Ca CO3
Solubility of Mg(OH) 2

0.6
0.2

Na+

Present in raw water

From Na2CO3 added
M+, not including excess lime

0.3

Ca

Na

ANIONS

2.0
3.1
(meq/L)

OH
OH-

Excess lime, Ca(OH)2

Solubility of Mg(OH) 2

1.25
0.2

CO32SO4 2Cl-

Solubility of Ca CO3
Present in raw water
Present in raw water
M , not including excess lime

0.6
2.0
0.3
3.1

See the bar graph (2)

Recarbonation
1) converts the excess OH to CO32
Ca(OH)2 + CO2 CaCO3(s) + H2O
Excess OH = OH from excess lime + OH from Mg(OH) 2
=
1.25 meq/L
+
0.2 meq/L

= 1.45 meq/L

1.45 meq
22 mg
= --------------- (---------- CO2 ) = 31.9 mg/L of CO2
L
meq
- Draw a bar graph for the softened water after recarbonation and filtration assuming that
one-half of the alkalinity is in the bicarbonate form. See the bar graph (3)
12

9-Softning_F12

2) After second-stage processing, final recarbonation convert of remaining CO32 to

HCO3CaCO 3 + CO 2 + H2O Ca(HCO3) 2
0.6
0.6
MgCO 3 + CO 2 + H2O Mg(HCO3) 2
0.2
0.2
22 mg
()(0.8 meq/L)(--------- CO2 ) = 8.8 mg/L of CO2
meq
Total CO2 Reacted = 31.9 + 8.8 = 40.7 mg/L
= 40.7 mg/L (8.34 lb/MG per mg/L)
= 340 lb CO2 / MG

(d) Draw a bar graph for the softened water after recarbonation and filtration.
CATIONS
Ca 2+
Mg2+
Na+

Solubility of Ca CO3
Solubility of Mg(OH) 2
Present in raw water + From Na2CO3
added
+
M , not including excess lime

(meq/L)
0.6
0.2
2.3
3.1

ANIONS
CO32HCO3SO4 2Cl-

Solubility of Ca CO3
From Ca(HCO3) 2 and Mg(HCO3) 2
Present in raw water
Present in raw water

(meq/L)
0.4
0.4
2.0
0.3

M-, not including excess lime

3.1

13

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14

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A single-stage calcium carbonate softening plant

A two-stage excess lime softening plant

15

9-Softning_F12

A split-treatment softening plant

CO2

Homework #7 is due one week from today!

16