PROGRAM STUDI REKAYASA INFRASTRUKTUR LINGKUNGAN

FAKULTAS TEKNIK SIPIL DAN LINGKUNGAN

INSTITUT TEKNOLOGI BANDUNG
Semester I 2023/2024
IL-3102 Satuan Proses

KULIAH MINGGU KE-11

Softening
Rabu, 1 November 2023
(Perkuliahan dilaksanakan secara Luring)

Disampaikan:
Dr. Ir. I Made Wahyu Widyarsana, ST. MT.
(Dosen Program Studi Rekayasa Infrastruktur Lingkungan, FTSL-ITB)
E-mail: wahyu.labb3@gmail.com; Hp. 08156262892

RPS (Setelah UTS)

◼ Minggu ke-9 : Disinfection
◼ Minggu ke-10 : Water softening (1)
◼ Minggu ke-11 : Water softening (2)
◼ Minggu ke-12 : Oxidation process (1)
◼ Minggu ke-13 : Oxidation process (2)
◼ Minggu ke-14 : Combustion (1)
◼ Minggu ke-15 : Combustion (2) atau
Praktikum/Tutorial/Quiz/Presentasi
◼ Minggu ke-16 : UAS

Catatan:
✓ Praktikum/Tutorial/Quiz/Presentasi akan disisipkan sewaktu-waktu
diperlukan
✓ Literasi materi setiap minggu

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Metode Pembelajaran

1. Kuliah offline, hybrid, online (informasi

diakses di six dan edunex)
2. Tutorial/quiz/literasi/tugas lain
(dikumpulkan di edunex)
3. Praktikum (ditentukan kemudian)

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Private Water System Resources

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 Hard water

What is "Hard Water"?

◼ Perhaps you have on occassion noticed mineral deposits on your
cooking dishes, or rings of insoluble soap scum in your bathtub.
These are not signs of poor housekeeping, but are rather signs
of hard water from the municipal water supply.
◼ Hard water is water that contains cations with
a charge of +2, especially Ca2+ and Mg2+.
◼ These ions do not pose any health threat, but they can engage
in reactions that leave insoluble mineral deposits. These
deposits can make hard water unsuitable for many uses, and so
a variety of means have been developed to "soften" hard water;
i.e.,remove the calcium and magnesium ions.

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 water hardness

➢ Hard water is water contaminated with compounds of

calcium and magnesium. Dissolved iron, manganese,
and strontium compounds can also contribute to the
"total hardness" of the water, which is usually
expressed as ppm CaCO3.

➢ Water with a hardness over 80 ppm CaCO3 is often

treated with water softeners , since hard water
produces scale in hot water pipes and boilers and
lowers the effectiveness of detergents.

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Table 1. Hardness Classification
----------------------------------------------------------
Concentration of
hardness minerals milligrams per
in grains per liter (mg/l) or
gallon (gpg) Level of Hardness parts per million (ppm)
----------------------------------------------------------
below 1.0 soft less than 17
1.0 to 3.5 slightly hard 17 to 60
3.5 to 7.0 moderately hard 61 to 120
7.0 to 10.5 hard 121 to 180
above 10.5 very hard more than 180
----------------------------------------------------------

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Problems with Hard Water
◼ Mineral deposits are formed by ionic reactions resulting in
the formation of an insoluble precipitate. For example,
when hard water is heated, Ca2+ ions react with
bicarbonate (HCO3-) ions to form insoluble calcium
carbonate (CaCO3), as shown in Equation 1.

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8
◼ This precipitate, known as scale, coats the vessels in which the
water is heated,
◼ reduce the efficiency of heat transfer
◼ serious effect for industrial-sized water boilers
◼ scale can accumulate on the inside of appliances, such as
dishwashers, and pipes.

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Softening

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Neutralization
CO2+Ca(OH)2 → CaCO3(s) + H2O

Ca+2 Precipitation at pH 10
Ca+2 +2HCO3-+Ca(OH)2 → 2CaCO3(s) + 2H2O

Mg+2 Precipitation at pH 11
Mg+2 +2HCO3-+Ca(OH)2 → 2MgCO3 + CaCO3(s) + 2H2O
Mg+2 + CO3= +Ca(OH)2 → Mg(OH)2((s) + CaCO3(s)

Ionic Balance: addnon non hardness ionic (Na+) :

Mg+2 +NaOH → Mg(OH)2((s) + Na +
Ca+2 +Na2CO3 → CaCO3(s) + 2Na+

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 Precipitation
◼ For large-scale municipal operations, a process known as the
"lime-soda process" is used to remove Ca2+ and Mg2+ from the
water supply.
◼ The water is treated with a combination of slaked lime,
Ca(OH)2, and soda ash, Na2CO3. Calcium precipitates as
CaCO3, and magnesium precipitates as Mg(OH)2. These solids
can be collected, thus removing the scale-forming cations from
the water supply.
◼ To see this process in more detail, let us consider the reaction
for the precipitation of Mg(OH)2.
◼ Consultation of the solubility guidelines in the experiment
reveals that the Ca(OH)2 of slaked lime is moderately soluble in
water. Hence, it can dissociate in water to give one Ca2+ ion
and two OH- ions for each unit of Ca(OH)2 that dissolves.

◼ The OH- ions react with Mg2+ ions in the water to form
the insoluble precipitate. The Ca2+ ions are unaffected
by this reaction, and so we do not include them in the
net ionic reaction. They are removed by the separate
reaction with CO32- ions from the soda ash.

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 Ion-exchange
◼ Ion-exchange devices consist of a bed of plastic
(polymer) beads covalently bound to anion groups,
such as -COO-.
◼ The negative charge of these anions is balanced by
Na+ cations attached to them. When water
containing Ca2+ and Mg2+ is passed through the ion
exchanger, the Ca2+ and Mg2+ ions are more
attracted to the anion groups than the Na+ ions.
◼ Hence, they replace the Na+ ions on the beads, and
so the Na+ ions (which do not form scale) go into
the water in their place.

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 The ion exchange process
◼ Calcium (Ca2+) and magnesium (Mg2+) ions that
cause water hardness can be removed fairly easily by
using an ion exchange procedure.
◼ Water softeners are cation exchange devices. Cations
refer to positively charged ions. Cation exchange
involves the replacement of the hardness ions with a
nonhardness ion.
◼ Water softeners usually use sodium (Na+) as the
exchange ion. Sodium ions are supplied from
dissolved sodium chloride salt, also called brine. In
the ion exchange process, sodium ions are used to
coat an exchange medium in the softener.
◼ The exchange medium can be natural "zeolites" or
synthetic resin beads that resemble wet sand.

The exchange medium can be

natural "zeolites" or synthetic resin
beads that resemble wet sand.

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◼ Softening Process
NaZeolite + Ca2+ --> CaZeolite + Na+
and
NaZeolite + Mg2+ --> MgZeolite + Na+

◼ Recharging Process
NaCl + CaZeolite --> NaZeolite + CaCl
and
NaCl + MgZeolite --> NaZeolite + MgCl

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 Ion exchange softeners replace Ca++ and Mg++ with Na+ ions.
Zeolite medium is recharged with Na+ by NaCl brine when depleted.

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 Ion Exchange Water Softeners

◼ Exchange sodium ions for calcium and magnesium

ions in water
◼ May be dietary hazard - hypertension (adds 140
mg/l of sodium in “Hard” water)
◼ Use potassium salt (KCl) for health reasons

◼ Many people with high blood pressure or other

health problems must restrict their intake of sodium.

◼ Because water softened by this type of ion exchange

contains many sodium ions, people with limited
sodium intakes should avoid drinking water that
has been softened this way. Several new techniques
for softening water without introducing sodium ions
are beginning to appear on the market.

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 Types of water softening
equipment available

Water softeners are classified in five different categories:

◼ Manual: There are several types of manual softeners. The
operator opens and closes valves to control the frequency, rate
and time length of backflushing or recharging.
◼ Semi-automatic: The operator initiates only the recharging
cycle. A button is pushed when the softener needs recharging
and the unit will control and complete the recharging process.
◼ Automatic: The automatic softener usually is equipped with a
timer that automatically initiates the recharging cycle and every
step in the process. The operator needs only to set the timer
and add salt when needed. It is the most popular type of
softener used.

Types of water softening

equipment available

◼ Demand initiated regeneration (DIR): All operations are

initiated and performed automatically in response to the water
use demand for softened water. DIR systems generally have
two softening tanks and a brine tank. While one tank is
softening the other tank is recharging.

◼ Off-site regeneration (generally rental units): A used

softening tank is physically replaced with a recharged tank.
Spent softening tanks are then recharged at a central location.

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Ion Exchange Water
Softener with
Sensor- Controlled
Recharge

Softener Selection Considerations

◼ Required grain capacity

◼ Daily water use (household population)
◼ Water hardness
◼ Desired regeneration schedule
◼ Initial cost
◼ Water conservation
◼ Other (Iron removal, etc.)

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 Ion Exchange Water
Softener Capacity
◼ Rated by grains of hardness treated between
regenerations

Example:
Water hardness = 200 mg/l
Softener Capacity = 2000 gr
Household Population = 4 persons

Calculate:
Water Use = 4 persons x 200 l/person-day = 800 l/day
Daily Hardness Treated = 800 l/day x 200 mg/l = 160 gr/day
Regeneration Interval = 2000 gr/ 160 gr/day = 12.5 days

2 minggu → 2240 gr 1 KK 5 orang, 150 l/o/hari → 13.3 hari

1 bulan → 4800 gr 1 KK 6 orang, 150 l/o/hari → 11.1 hari

Recommended Softener Sizes

Pump Capacity Softener Capacity Water Hardness
(l/det) (gr) (mg/l)
50 750 350
80 1000 500
120 1500 850
140 2000 1200
200 3000 1500

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 Ion Exchange Water Softener
Recharge Control Method
Water Initial Cost
Use
-
+
-Time Clock
-Flow Meter
-Hardness
-
- Sensor +

Water Softening

◼ Permanent magnet water softeners

don’t work
◼ Electrostatic and catalytic descalers
may “descale” water, but don’t
soften it
◼ Scale will not buildup on pipes, water
heater elements, bathtubs etc.
◼ Sudsing action of soaps is not improved

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Typical Programmable Water Softener
Controller

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 Reactions

◼ CO2+Ca(OH)2→CaCO3+H20
◼ Ca(HCO3)2+Ca(OH)2=2CaCO3+2H20
◼ Mg(HCO3)2+Ca(OH)2=MgCO3+CaCO3+2H20
◼ MgCO3+Ca(OH) 2=Mg(OH)2+2CaCO3
◼ MgSO4+Ca(OH) 2=CaSO4 + Mg(OH)2

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◼ CaSO4+Na2CO3=CaCO3 + Na2SO4
◼ CaCl2+Na2CO3=CaCO3 + 2NaCl
◼ MgSO4+Ca(OH)2=CaSO4 + Mg(OH)2
◼ MgCl2+Ca(OH)2= Mg(OH)2 + CaCl2

◼ CO2+Ca(OH)2→Ca+2+2OH-
◼ CO2+2OH- →HCO3-
◼ HCO3-+OH- →CO3-2+H20
◼ Ca+2 +CO3-2 → CaCO3
◼ Mg+2 + 2OH- →Mg(OH)2

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 Pretreatment and other
variations

Prior to softening some preliminary treatment may be

advisable if
1. Raw water turbidities exceed 3,000 NTU at times
2. Raw water has high concentration of free carbon
dioxide (more than 10 mg/l)
3. The raw water is high in organic colloids of a type that
impedes crystallization of calcium carbonate
4. Raw water quality is highly variable over short periods
of time
5. Recalcining of sludge is to be practiced

Variation of process
◼ Single or two stage recarbonation ater conventional
lime-soda treatment
◼ Sludge recirculation
◼ Excess lime treatment with split treatment or
recarbonation
◼ Post-treatment with polyphophates
◼ Coagulation with alum, activated silica, or polymers
◼ The use of three-stage treatment
◼ The substitution of cation exchangers for soda ash to
remove non carbonate hardness
◼ The use of caustic soda instead of soda ash

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◼ CO2+2NaOH→Na2CO3+H20
◼ Ca(HCO3)2+2NaOH=CaCO3+Na2CO3+2H20
◼ Mg(HCO3)2+4NaOH=Mg(OH)2+2Na2CO3+2H20
◼ MgSO4+2NaOH=Mg(OH)2 + Na2SO4

Systems expressing hardness

of water
◼ German degree = Ca and Mg equivalent
with 10 mg CaO/liter
◼ French degree = Ca and Mg equivalent
with 10 mg CaCO3/liter
◼ English degree = one grain (0.06480 g)
of CaCO3 per gallon (3.785 L)
◼ USA = ppm (mg/L) CaCO3

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Expressing hardness in
milliequivalent/liter
1 milli-equivalent per liter =

- 2.8 German degree

- 5.0 French degree
- 3.5 English degree
- 50 mg CaCO3/liter

< 2 meq/L → soft water

> 5 meq/L → hard water

Total hardness = amount of Ca and Mg non

carbonate hardness + carbonate hardness.

Carbonate hardness = Ca and Mg equivalent to

bicarbonate content

The difference between total hardness and

bicarbonate (also called carbonate) hardness
is the non carbonate hardness, which
corresponds with ions like Cl-, and SO4--

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 HCO3-
I
Total hardness

Ca+2 Mg+2

HCO3-
II Total hardness

Ca+2 Mg+2

Solubility in water
Substance mg/l meq/l mg CaCO3/l

Ca(OH)2 1280 34.9 1730

CaCO3 15 0.3 15

Ca3(PO4)2 Nearly insoluble

Mg(OH)2 8.4 0.29 14.5

MgCO3 110 2.62 131

Mg3(PO4)2 Nearly insoluble

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 Disadvantage of phosphate method
- Rather expensive (cost of sodium
orthophosphate)
- Treated water will contain some rest of
PO43-
- For drinking water it is not necessary
and even not reccomendable to remove
all hardness

Lime soda process

I CO2+Ca(OH)2→CaCO3+H20 1
II Ca(HCO3)2+Ca(OH)2=2CaCO3+2H20 1

IIIa Mg(HCO3)2+Ca(OH)2=MgCO3+CaCO3+2H20
IIIb MgCO3+Ca(OH)2=Mg(OH)2+2CaCO3
III Mg(HCO3)2+2Ca(OH)2=Mg(OH)2+2CaCO3+2H20 2

IV CaCl2+Na2CO3=CaCO3 + 2NaCl 1

Va MgCl2+Ca(OH)2=CaCl2 + Mg(OH)2
Vb CaCl2+Na2CO3=CaCO3 + 2NaCl
V MgCl2+Ca(OH)2+Na2CO3=CaCO3 + Mg(OH)2 + 2NaCl 1 1
II, III carbonate hardness reactions needed Ca(OH)2 in meq
IV, V non carbonate hardness reaction needed Na2CO3 in meq

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 Lime soda process I II V

Lime needed : [CO2] +[HCO3-]+ [Mg+2]

Soda needed : [Ca+2] - [HCO3-] + [Mg+2]
CO2 HCO3-
I IV V

Ca+2 Mg+2

CO2 HCO3-
II

Ca+2 Mg+2 Lime needed : [CO2] +[HCO3-]+ 2[Mg+2]

I II III

Sodium hydroxide-soda process

Advantages
- Dosage of NaOH solutions is very
simple
- By using NaOH the amount of sludge is
much less than with Ca(OH)2 as the
precipitating agent)

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 NaOH process
I CO2+2 NaOH→Na2CO3+H20 1
II Ca(HCO3)2+ 2NaOH =CaCO3+Na2CO3+2H20 1

IIIa Mg(HCO3)2+ 2NaOH =MgCO3+Na2CO3+2H20

IIIb MgCO3+ 2NaOH =Mg(OH)2+Na2CO3
III Mg(HCO3)2+ 4NaOH =Mg(OH)2+2Na2CO3+2H20 2

IV CaCl2+Na2CO3=CaCO3 + 2NaCl 1

V MgCl2+ 2NaOH = NaCl + Mg(OH)2 1

II, III carbonate hardness reactions needed NaOH in meq
IV, V non carbonate hardness reaction needed Na2CO3 in meq

NaOH process I II V

NaOH needed : [CO2] +[HCO3-]+ [Mg+2]

Soda needed : ([Ca+2] - HCO3- ) – ([CO2] +[HCO3-])
CO2 HCO3- [Ca+2] - [CO2] - 2[HCO3-]
I
IV I, II

Ca+2 Mg+2

CO2 HCO3-
II

Mg+2
Ca+2 NaOH needed : [CO2] +[HCO3-]+ 2[Mg+2]

I II III

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◼ CaSO4+Na2CO3=CaCO3 + Na2SO4
◼ CaCl2+Na2CO3=CaCO3 + 2NaCl
◼ MgSO4+Ca(OH)2=CaSO4 + Mg(OH)2
◼ MgCl2+Ca(OH)2= Mg(OH)2 + CaCl2

Diketahui air mengandung ion

◼ Cl=142 mg/l,

◼ HCO3-=183 mg/l

◼ Ca++ = 120 mg/l

◼ Mg++=36 mg/l

◼ CO2 terlarut = 66 mg/l

Harga bahan kimia

◼ Na2CO3 = Rp. 4500/kg

◼ NaOH = 4000/kg

◼ Ca(OH) = 2500/kg

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1. Hitung tingkat kesadahan yang dapat dicapai
dengan metode pengendapan yang paling murah.
Jawaban didasarkan atas perhitungan dan reaksi-
reaksi
2. Hitunglah tingkat kesadahan yang dapat dicapai
dalam proses pelunakan menggunakan Ca(OH)2 jika
diketahui bahan proses ini memerlukan kelebihan
dosis Ca(OH)2 sebanyak 18,5 mg/l
3. Idem soal 2 menggunakan NaOH jika diperlukan
kelebihan dosis NaOH sebesar 16 mg/l

◼ Cl-=142 mg/l =142/35.5 = 4 meq/l

◼ HCO3-=183 mg/l = 183/61 = 3 meq/l
◼ Ca2+ = 120 mg/l = 120x2/40=6 meq/l
◼ Mg2+ = 36 mg/l = 36x2/24 = 3 meq/l
◼ CO2 = 66 mg/l = 66x2/44 = 3 meq/l

Ca2+ Mg2+ > HCO3- → bukan hanya kesadahan

sementara
Kesadahan total = 9 meq/l
Kesadahan sementara = 3 meq/l
Kesadahan tetap = 6 meq/l

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Total Ca(OH)2 yang dibutuhkan
333+18,5 = 350 mg/l

Naik 350/333 = 1,05

Ksp CaCO3 <→ Ca2+ + CO3=

pada suhu tertentu adalah 0,3 meq/l
=[Ca2+][CO3=]/[CaCO3]
dengan memperhatikan

Ca(OH)2 = Ca2+ + OH-

350 350
---- mmol/l ----- mmol/l
74 74
Dengan kenaikan 1,05 pada ion Ca
maka Ksp → 0,3 x 1,05 = 0,315 meq/l

Mg(OH)2 = Mg2+ + OH-

Ksp = 0,24 meq/l

Total 0,555 meq/l = 1,64 D CaCO3

1 D = 10 mg/L CaCO3 = 10/(40+12+48)*2

= 0,2 meq/L CaCO3

Ca(OH)2 = Ca2+ + 2OH-

18,5 mg
18,5 x 2
--------- = 0,5 meq/L
40+34
Tingkat kesadahan 0,5/0,2 = 2,5 D

NaOH = Na+ + OH-

16 mg
16/40 =
0,4 meq

Kesadahan 0,4/0,2 = 2 D

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35
 Tugas (1 sks)
◼ LITERASI ILMIAH: terkait materi hari ini
◼ Dikumpulkan sebelum kuliah berikutnya di Edunex (Submission nya
di Minggu pemberian tugas, contoh tugas minggu ini (minggu ke-
11) disubmit di Edunex minggu ke-11.
◼ Format:
- Word (min. 5 halaman, spasi max 1,5, time new roman 11 pt)
- Ppt (min. 10 halaman, spasi max. 1,5, arial 18 pt)
- Wajib menyertakan link video terkait pada tugas di atas

Catatan:
Tugas mingguan ini akan menjadi nilai tugas (proporsi tersendiri dalam
penilaian), dan sebagai nilai tambah bagi mahasiswa yang nilainya kurang.

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Diskusi & Tanya Jawab

TERIMA KASIH

Dr. Ir. I Made Wahyu Widyarsana, ST. MT.

HP. 08156262892 (sms/wa only)

E-mail: wahyu.labb3@gmail.com

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