-

Stream water hardness is the total

concentration of cations, specifically calcium
(Ca2+ ),magnesium (Mg2+), iron (Fe2+),
manganese (Mn2+) in the water.
Water rich in these cations is said to be
hard. Stream water hardness reflects the
geology of the catchment area.
Sometimes it also provides a measure of the
influence of human activity

For instance, acid mine drainage often

results in the release of iron into a stream.
The iron produces extraordinarily high
hardness is a useful water quality indicator.
Hardness is a reflection of the amount of
calcium and magnesium entering the
stream through the weathering of rock
such as limestone (CaCO3).

Many people object to water containing harness greater than 150 mg/L
as CaCO3, suppliers of public water have considered to soften the
water (remove hardness) to < 120 mg/L as CaCO3.
Total Hardness (TH) = Ca2+ + Mg2+
Total Hardness (TH):
1. Carbonate Hardness (CH) - Combination of Ca and Mg ion with
CO32-, or HCO-3 ion. Also called as temporary hardness because can
be removed by heating.
2. Non-carbonate Hardness (NCH) - associated with other anions,
Cl-, SO42-, or NO-3 . Called as permanent hardness. Defined as the
total hardness in excess of the alkalinity. If the alkalinity total
hardness, there is no NCH.
TH = CH + NCH

Source: combination of Ca dan Mg ions

with CO32- ion or HCO3-.

Carbonate components can be removed

through softening such as boiling,
addition of lime

Water hardness are removed as the

carbonate components in water

precipitate.

Ca 2+

Ca(HCO3)2

Mg 2+

CaCO3

+ HCO3-

Mg(HCO3)2

CO32-

MgCO3

Source: Combination of Ca & Mg ions with Cl-, SO42-, or NO-3

ion.

Non-Carbonate ion cannot be removed through boiling, but it

can be removed through soda-ash softening or lime-soda

softening.

Hardness of element in mg/L as CaCO3

mg/L element X = conc. Of X (mg/L) (50 mg CaCO3/meq)
as CaCO3

(EW of X (mg/meq))

Total Hardness CaCO3 : = Ca2+ + Mg2+ (the predominant

Contributors)

Ca 2+

Mg 2+

CaCl2

CaSO4

Ca(NO3)2

Cl-

SO42-

MgCl2

CaSO4

NO3-

Mg(NO3)2

Unit of hardness: mg/L as CaCO3 .

Hardness classification:
soft
50mg/l asCaCO3
moderately hard
50-150mg/l asCaCO3
hard
150-300 mg/l as CaCO3
very hard
>300 mg/l as CaCO3

Find the equivalent weight (EW) of each of the

following: Ca2+, CO32-,CaCO3.
Solution:

Equivalent weight was defined as

EW = atomic or molecular weight / n

(valence)
units: grams/equivalent (g/eq) or miligrams/miliequivalent
(mg/meq)
For calcium, n=2 (valence or oxidation state in water). Atomic
weight = 40.08, therefore the EW is then
EW = 40.08/2 = 20.04 g/eq or mg/meq

For carbonate ion (CO32-), the oxidation state of 2- is used for n

since the base CO32- can potentially accept 2 H+. The
molecular weight is 60.01. Therefore,
EW = 60.01/2 = 30 g/eq or mg/meq

In CaCO3, n=2 since it would take 2H+ to replace the cation

(Ca2+) to form carbonic acid, H2CO3. the MW is 100.
Therefore,
EW = 100/2 = 50 g/eq or mg/meq

Constituent

mg/L

Ca2+

95.2

Mg2+

13.5

Na+

25.8

Cl-

67.8

SO2-4

76.0

NO -3

15.3

Al 2(SO4)3

18.4

MW

EW

mg/L as CaCO3

A sample of groundwater has 120 mg/L of Ca2+

and 20 mg/L of Mg2+. Express it hardness in unit
of mg/L as CaCO3.
Solution:

recalled:

Mg/L of X = concentration of X (mg/L) (50 mg /meq CaCO3 )

as CaCO3

(equivalent weight of X (mg/meq))

1. Convert Ca2+ and Mg2+ to mg/L as CaCO3

Ca2+ : MW = 40, n=2, EW=40/2 =
Mg2+ : MW = 24.3, n=2, EW=24/2 =

Now, find the mg/L as CaCO3 of cations

Ca2+ =
Mg2+ =

Total Carbonate Hardness = Ca2+ + Mg2+

=
=

Is measured to determine the ability of a

stream to resist changes in pH.
Alkalinity results from the dissolution of
calcium carbonate (CaC03) from limestone
bedrock which is eroded during the natural
processes of weathering
Alkalinity values of 20 -200 ppm are common
in freshwater ecosystems. Alkalinity levels
below 10 ppm indicate poorly buffered
streams.
These stream are the least capable of resisting
changes in pH, therefore they are most
susceptible to problems which occur as a result
of acidic pollutants

Is a measure of the acid-neutralizing capacity of water to

the equivalence point of carbonate or bicarbonate.

This ability to neutralize acid, or H+ ions, is particularly important

in regions affected by acid rain.

Carbonate species which contribute to alkalinity are as the

following:
Hydroxyl (OH-), Ion Carbonate (CO32-), Ion Bicarbonate (HCO3-), Carbon
dioxide (CO2)
Alkalinity (mol/L) = [HCO3-] + 2[CO32-] + [OH-] [H+]
Alkalinity (eq/L or mg/L as CaCO3) = (HCO3-) + (CO32-) + (OH-) (H+)
For nearly neutral water, the concentrations of H+ and OH- are negligible.

15

Nitrogen is an essential nutrient that is

required by all plants and animals for the
formation of amino acids.
In its molecular form, nitrogen cannot be
used by most aquatic plants, therefore it
must be converted to another form.
One such form is ammonia (NH3). Ammonia
may be taken up by plants or oxidized by
bacteria into nitrate (NO3-) or nitrite (NO2-).
Of these two forms, nitrate is usually the
most important.

It is a measure of the quantity of oxygen

used by microorganisms (eg.aerobic
bacteria) in the oxidation of organic matter.
In other words: BOD measures the change
in dissolved oxygen concentration caused
by the microorganisms as they degrade the
organic matter.
High BOD is an indication of poor water
quality

BOD dalam sample yang dicairkan dikira sebagai:

BOD

DOi DO f
P

DOi DO awal (initial DO)

DO f DO akhir ( final DO)
P faktor pencairan sampel

Persamaan BOD tanpa pembenihan air kawalan.

(Unseeded dilution water)

BOD

[( DOi DO f ) ( BOi BO f )] f
P
DOi DO awal (initial DO)
DO f DO akhir ( final DO)
BOi DO awal air kawalan
BO f DO akhir air kawalan
P faktor pencairan sampel

Persamaan BOD dengan pembenihan air kawalan. (Seeded dilution

water)

Latihan 3

Dengan menggunakan persamaan BOD, kira nilai

BOD suatu sample yang mempunyai nilai-nilai
berikut:
DOi = 7.0mg/l
DOf = 6.3mg/l
BOi = 7.1mg/l
BOf = 7.0mg/l
P = 1/10
f = 1.0
BOD =

Bahan organik O2 nutrien biojisim baru (new biomass) CO2

H 2O produk stabil

Proses BOD adalah satu proses yang amat perlahan dan

secara teorinya memerlukan masa yang infiniti umtuk
melengkapkan proses.
Dalam masa 20 hari, pengoksidaan organic berkarbon
(carbonaceous organic) adalah sekitar 95-99% lengkap.
Dalam masa 5 hari, pengoksidaan adalah sekitar 60-70%
lengkap.
20C diambil kerana ia adalah nilai suhu purata air sungai
beriklim sederhana. Tambahan pula, ia mudah dicapai
menggunakan incubator.
Nilai BOD yang berbeza didapati bagi setiap suhu
pengeraman yang berbeza kerana kadar tindakbalas biokimia
adalah bergantung kepada suhu.

Tindakbalas kinetik BOD ditunjukkan sebagai tindakbalas

tertib pertama seperti berikut:

dLt

Lt
dt
dLt
kLt
dt

Pers. 1

Lt = jumlah BOD yang tinggal pada masa t

Lo = BOD muktamad
k = pemalar kadar tindakbalas, hari-1, (base e)
K = k/2.303, pemalar kadar tindakbalas, hari-1 (base 10)

Kamirkan pers. 1

Lt

Lo

t
dLt
k dt
o
Lt

lnLt

Lt
Lo

kt

Pers. 2

ln Lt ln Lo kt

Lt
ln kt
Lo

Lt

Lo

kt
e 10 Kt

Pers. 3

Lt Lo e

kt
Pers. 4

y, jumlah BOD yang dikeluarkan pada bila-bila masa t

BODt, yt = Lo Lt
= Lo Lo e-kt
= Lo (1 e-kt)

BOD 5 hari :

y5 = Lo L5
= Lo (1-e-5k)

Dengan menggunakan persamaan:

kT = k20 (T-20)
Di mana = 1.047

nilai pemalar tindakbalas k boleh dianggarkan

pada suhu-suhu yang berlainan.

Latihan 4
Tentukan BOD 1 hari dan BOD akhir (ultimate BOD, Lo) bagi satu
sample air sisa. Diberi BOD5,20C air sisa tersebut adalah 200 mg/l
dan k = 0.23 d-1

Tentukan BOD ultimate

Lt = Lo e-kt
y5 = Lo L5
= Lo (1 - e-kt)
200 = Lo (1 - e-5(0.23))
= Lo (1- 0.316)
Lo =
Tentukan BOD1, L1
Lt = Loe-kt
L1 = 293 (e-0.23(1))
= 293 (0.795)
L1 = 233 mg/l
Y = L o - L1
= (293-233) mg/l
=

According to Thomas,
(1-e-kt) = kt (1+kt/6)-3
Therefore
BODt=Lo(1-e-kt)
BODt=Lo(kt)[1+(1/6)kt]-3

.....(1)

By rearranging terms & taking the cube root of both sides,

equation (1) can transformed to:
(t/BODt)1/3=(kLo)-1/3 + (k)2/3/6(Lo)1/3 (t)

....(2)

A plot of (t/BODt)1/3 versus t is linear. The

defined as:

intercept is

A = (kLo)-1/3

.(3)

slope is defined by:

B = (k)2/3/6(Lo)1/3

a
b

C =(kLo)-1/3

Recalled , y = c + mx

x=t

.(4)

m=a/b = (k2/3/6Lo1/3)

Solving Lo1/3 in Eq.(3) substituting into Eq. (4) and solving for
k yields:

k= 6(B/A) (5)

Likewise, substituting Eq. (5) into Eq.(3) and solving for Lo

yields:

Lo = 1/6(A)2(B) (6)

The following data were obtained from an

experiment to determine the BOD rate constant
and ultimate BOD for an untreated wastewater:
Time (day)

10

BOD
(mg/L)

125

200

220

230

237

Solution:

Calculate values of (t/BODt)1/3 for each day.

Time (day)

10

BOD (mg/L)

125

200

220

230

237

0.252

0.271

0.301

0.326

0.348

(t/BODt)1/3

Plot (t/BODt)1/3 versus t on graph paper and draw

the line of best fit by eye.

0.5
0.4

B= 0.0124

0.3

0.2

A= 0.224

0.1
0

10

Time (t)

Determine the intercept (A) and slope (B)

from the plot.
A = 0.224
B = (0.348-0.224)/(10-0)
= 0.0124

Calculate k and Lo using the following

formula

k = 6 (B/A)

Lo = 1/ 6(A)2(B)

Therefore:
k= 6(B/A)
= 6(0.0125/0.224)
= 0.335 / day
Lo = 1/6(A)2(B)
= 266 mg/L