Kimia Air

Hidrosfer/Kimia Air - 1
2HCO
3
-
+ hv
Fotosintesis
{CH
2
O} +
O
2
(g) + CO
3
2-
CO
3
2-
+ H
2
O
Asam-basa
H CO
3
-
+ OH
-
Ca
2-
+ CO
3
2-

pengendapan
CaCO
3
-
(s)

{CH
2
O} + SO
4
2-
+ 2H
+ mikroba
H
2
S +
H
2
O + CO
2
(g)
O
2
CO
2
Cd
2+
R
e
d
u
k
s
i
-
o
k
s
i
d
a
s
i

NH
4
+
NO
3
-
Lindi
Penyerapan
Lumpur
Dasar Kimia Air

Suber Sepesi Kimia dalam Air Alami
Origin Positive Ions Negative Ions
Contact of water with minerals,
soils, and rocks
Ca+2, Fe+2
Mg+2, Mn+2
K+, Na+, Zn+2
HCO3 -, CO3
-2
Cl-, F-, NO3 -
PO4 -3, OH -, SO4 H2BO3 -,
H3SiO4
The atmosphere, in rain H+ HCO3 -, Cl-, SO4
Decomposition of organic matter
in the environment
NH4 +, H+, Na+
Cl-, HCO3 -, OH -, NO2 -, NO3 -
, HS-Organic radicals
Municipal, industrial, and
agricultural sources and other
human activity

Inorganic ions,
including a
variety of heavy
metals

Inorganic ions, organic
molecules, color


Parameter Kunci Kualitas Air untuk Berbagai Keperluan
Public water supply Industrial water supply Agricultural water
supply
Aquatic life and wildlife Recreation and
aesthetics
Coliform bacteria
Turbidity
Colour
Taste-odour
Trace metals
Dissolved solids
Trace organics
Chlorides
Fluorides
Sulphates
Nitrates
Cyanides
Radioactivity
Processing (except foods)
pH
Turbidity
Colour
Hardness
Alkalinity/acidity
Dissolved solid
Suspended solids
Trade metals
Trade organics
Cooling
pH
Temperature
Silica
Aluminium
Iron
Manganese
Hardness
Alkalinity/acidity
Sulphates
Dissolved solids
Suspended solids
Sanitary (same as for
public supply
Farmstead:
(same as for public
supply)
Livestock: (similar to
that for public supply)
Irrigation:
Dissolved solids
Specific conductance
Sodium
Calcium
Magnesium
Potassium
Boron
Chlorides
Trace metals
Temperature
DO
pH
Alkalinity/acidity
Dissolved solids
Salinity
Carbon dioxide
Turbidity
Colour
Settleable materials
Floating material
Tainting substances
Toxic materials
Nutrients
Substances adversely
affecting wildlife
Recreation
Coliforms
Turbidity
Colour
pH
Odour
Floating materials
Settleable
materials
Nutrients
Temperature
Aesthetics
Turbidity
Colour
Odour
Floating materials
Settleable
materials
Nutrients
Temperature
Substances
adversely
affecting wildlife

Temperatur
Measured with a thermometer
Units are C
Range is <0 to ? (in Phoenix?)
Important because:
Temperature influences the amount and diversity of aquatic life
Helps us better understand other hydrology measurements like
Dissolved Oxygen (DO)
pH
Electrical Conductivity (EC)
Water temperature affects air temperature via evaporation & condensation
Possible indication of:
mixing of nutrient-rich waters
spawning

pH
pH is a measure of the acid content of water.
Measured with a pH meter or pH paper
Units are pH units are a logarithmic scale of hydrogen ion
concentration
Small change in pH can mean a big change in water quality

Transparensi (Turbidity)
Transparency is a measure of how clear the water is
Units are length, usually cm
Range is 0 to >100 cm
Measured with either a secchi disc or a
transparency tube
Important because:
suspended particles in water behave similarly to dust in
theAtmosphere
an increase in suspended particles reduces the depth to whichlight
can penetrate
this affects plants ability to photosynthesize
sediments can come from both natural and human sources

Electrical Conductivity (EC)
We call the amount of mineral and salt impurities in the water the total
dissolved solids (TDS)
We measure TDS and parts per million (ppm).
This tells us how many units of impurities there are for one million units
of water by mass.
We use an indirect measure to find the TDS of water. One way to
measure impurities is to see if it conducts electricity.
We use an EC meter to measure electrical conductivity.
Units are S/cm (microSiemens per cm). This is the same as a micromho.
Range is 0 to >2000 S/cm
We need to convert from S/cm to TDS, and this requires a conversion
factor. This conversion factor varies from 0.54 to 0.96, but 0.67 is commonly
used for an approximation
TDS (ppm) = Conductivity (S/cm) x 0.67

Kesetimbangan muatan
Aqueous solutions must be electrically neutral. In other words, the sum of
all negative charges must equal the sum of all positive charges.
One check on the quality of a water analysis is the charge-balance error,
calculated as follows:

There is always some error in the measurement of cation and anion
concentrations.
Thus, we cannot expect a charge-balance error of zero for any analysis.
The C.B.E. may be positive or negative, depending on whether cations or
anions are more abundant.
A reasonable limit for accepting an analysis as valid is 5%.

100 C.B.E.
+
=

a a c c
a a c c
z m z m
z m z m


Oksigen dalam air
Fungsi
pernafasan ikan
penguraian zat organik
konsumsi alga pada malam hari
Reoksigenasi badan air
Difusi dari atmosfer (O
2
= 20,95%)
Pergerakan air: Aliran dan gelombang
Angin
hasil fotosintesis alga
Juveniles
Adults
Stress
Mortality
Preferred

Dissolved Oxygen (DO)
DO is a measure of molecular oxygen (O2) dissolved in water
The amount of dissolved oxygen the water will hold is called the
solubility of dissolved oxygen. Factors that affect solubility are:
Water temp (Increase in temperature, decrease in DO)
Atmospheric pressure (higher elev., lower pressure, DO decreases)
Salinity (increase in salinity, DO decreases)
Units are mg/L or ppm
Dissolved oxygen can range from 0-18 mg/L, but most natural
watersystems require 5-6 mg/L to support a diverse population
Measured with a DO kit or a DO probe
Important because:
amount of DO in water determines what can live there
some organisms require higher oxygen levels than others
DO is affected by what lives in the water

Karbon dioksida dalam air
Sumber:
Udara (0.0350 % V)
Penguraian zat organik
Pelapukan Mineral Anorganik
Manfaat: fotosintesis pada alga
Konsentrasi yang tinggi berpengaruh pada
pernafasan binatang air (25 ppm mematikan ikan)
Kesetimbangan dengan udara-air

CO
2
(g) CO
2
(aq) ............. K
H

CO
2
(aq) HCO
3
-
+ H
+
......... K
a1

HCO
3
-
CO
3
2-
+ H
+
. ........ K
a2
H
2
O OH
-
+ H
+
.............. K
W
( ) 0 K K K 2 H K K K H
2 a 1 a HC 1 a HC W
3
=
+ +
2 2
CO CO
p p

Karbon dioksida dalam Air
0
0,2
0,4
0,6
0,8
1
1,2
2 3 4 5 6 7 8 9 10 11 12 13 14 15
CO2
HCO3
CO3
pH
f
r
a
k
s
i
| |
| | | |
o
CO
a a a
H
H K H K K
2
2
2
1 1 2
=
+ +
+
+ +
| |
| | | |
o
HCO
a
a a a
K H
H K H K K
3
1
2
1 1 2
=
+ +
+
+ +
| | | |
2 1 1
2
2 1
3
a a a
a a
CO
K K H K H
K K
+ +
=
+ +
o
Fraksi masing-masing spesi

Alkalinitas
Alkalinitas:
Kapasitas air untuk menetralkan asam
Penting untuk:
pengolahan air
mempelajari kimia dan biologi air
Alkalinitas dipengaruhi oleh:
CO
2
, HCO
3
-, CO
3
=
dan OH
-
(utama)
fosfat, silikat, asam organik, garam-garam asam
lemah, amonia
Alkalinitas tidak sama dengan kebasaan
Alakalinitas:
gambaran sumber karbon
anorganik
berperan dalam pertumbuhan
ganggang
ukuran kesuburan air
faktor kapasitas
Kebasaan:
tergantung pada kesetimbangan
asam basa
ditunjukkan oleh pH
faktor intensitas

Alkalinitas
Reaksi:
(1) CO
2
+ H
2
O HCO
3
-
+ H
+
..pk
a1
= 6,36
(2) HCO
3
-
+ H
2
O CO
3
=
.......pk
a2
= 10,32
(3) H
2
O H
+
+OH
-
.................pk
w
= 14

Alk. pp (pH=8.3)
Alk. total (pH= 4,3)
Pernyataan Alkalinitas
CO
3
2-
+ OH
-
HCO
3
-
CO
2
[Alk] = [HCO
3
-
] + 2[CO
3
2-
] +[OH
-
]
[C] = [CO
2
] + [HCO
3
-
] + [CO
3
2-
]

Alkalinity
Related to pH but different
Alkalinity is a measure of pH buffering capacity of
the water
What happens to the pH of water if acid is added?
The answer depends on:
How much buffering capacity (alkalinity) is in the water
How much acid is added
Measured with an alkalinity test kit
Expressed as amount of calcium carbonate
(CaCO3) in the water
Units are ppm or mg/L (1 ppm = 1 mg/L)

Alkalinity some examples
If water has a high alkalinity and acid is added, the alkalinity neutralizes
the acid. Some of the alkalinity will be used up, so the alkalinity will go
down. If more acid is added the alkalinity will continue to decrease.
Eventually, when the alkalinity is low enough, adding acid will cause the
pH to decrease.
When water has a high alkalinity we say it is well buffered. It resists a
decrease in pH when acidic water such as rain or snowmelt enters it.
Alkalinity comes from dissolved rocks, particularly limestone and soils
with CaCO3. It is added to the water naturally as water comes in contact
with rocks and soil. Water dissolves the CaCO3,,carrying it to lakes and
rivers.
If water has an alkalinity below about 100 mg/L as CaCO3, it is poorly
buffered and pH sensitive. A big rainfall or snowmelt could add enough
acid to lower the pH in a sensitive system. This could harm the organisms
that live there, esp. at certain times of the year (fish or insect larvae
hatching)

Nitrate (NO3-)
Nitrogen can have many chemical forms in water bodies:
Molecular nitrogen (N2)
as organic compounds (both dissolved and particulate)
as numerous inorganic forms such as
ammonium (NH4+)
Nitrite (NO2-)
Nitrate (NO3-)
Nitrate (NO3-) is usually the most important inorganic form
of nitrogen because it is an essential nutrient for the growth
and reproduction of many algae and other aquatic plants
Nitrogen is a limiting nutrient because in low amounts,
plants use up all the available nitrogen in the water and
cannot grow or reproduce anymore. So it limits the
amount of plants in the water

Nitrate (NO3-)
Nitrate (NO3-) is very difficult to measure directly, whereas
nitrite (NO2 -) is easier to measure
Nitrate kits convert the nitrate (NO3-) in the water sample to
nitrite (NO2-)
You will add a chemical to the water sample to accomplish
this conversion, and then a second chemical is added that
reacts with the nitrite (NO2-) to cause a color change
The measurement gives a combined concentration of nitrite (if
resent) and nitrate (which was converted to nitrite (NO2-) )
Units are mg/L
Most natural waters have nitrate levels under 1.0 mg/L
nitrate-nitrogen, but concentrations over 10 mg/L are found in
some areas. This affects whether you use a low-range or high
range test in the kit

Logam dalam Air
Logam dalam air terdapat sebagai ion dan akan
mengalami reaksi membentuk spesi paling stabil
yang tergantung pada sifat logam dan kondisinya
Reaksi yang terjadi
Hidrasi
Fe
3+
+ 6H
2
O Fe(H
2
O)
6
3+

Asam-basa
Fe(H
2
O)
6
3+
FeOH(H
2
O)
5
3+
+ H
+

Pengendapan
Fe(H
2
O)
6
3+
Fe(OH)
3
(s) + 3H
2
O + H
+
Redoks
Fe(H
2
O)
6
2+
Fe(OH)
2
(s) + 3H
2
O + H
+
+ e

Logam dalam Air

Logam dalam Air

Kesadahan
Pengaruh:
Sabun mengendap dan tidak berbusa
Pengerakan pada ketel uap
Ukuran kesadahan: mg CaCO
3
/L:
air lunak ( 0-75 mg /L)
air agak sadah (76 - 150 mg/L)
air sadah (151-300 mg/L)
Penyebab kesadahan
Penyebab pasangan Keter angan
Ca
2+
HCO
3
-
Kesadahan sementara
mg
2+
SO
4
=
Kesadahan tetap
Sr
2+
Cl
-
Fe
2+
NO
3
-
Mn
2+
SiO
3
-

Kesadahan
GH e f ppm mmol/l
German degree 1GH = 1 1,253 1,78 17,8 0,1783
English degree 1e = 0,798 1 1,43 14,3 0,142
French degree 1f = 0,560 0,702 1 10 0,1
CaCO3 (USA) 1 ppm = 0,056 0,07 0,1 1 0,01
mmol/l
1 mmol/l
= 5,6 7,02 10,00 100,0 1

Kesetimbangan Kalsium karbonat-karbondioksida
CaCO
3
+ CO
2
+ H
2
O Ca
2-
+ H CO
3
-

CO
2
CO
2
Lumpur
Ca
2-
CO
3
2-
| |
| |
2 a
1 a sp
2
2
3
`
K
K K
CO
CO Ca
K
2
=
=

+
Kesadahan

Kesadahan
Cara menghilangkan kesadahan
Penggunaan bikarbonat dan pemanasan
Ca
2+
+ 2 HCO
3
-
CaCO
3
(s) +CO
2
(g)+ H
2
O
Soda Kapur
Ca
2+
+ 2 HCO
3
-
+Ca(OH)
2
2 CaCO
3
(s) + H
2
O
Soda Abu
Ca
2+
+ CO
3
2-
2 CaCO
3
(s)
Ortofosfat
5 Ca
2+
+3 PO
4
3-
+ H
2
O 2 Ca
5
OH(PO
4
)
3
(s)
Penukar ion
Adsorben tanah liat, zeolit dsb.
Penambahan pengkompleks khelat

Senyawa Kompleks dalam Air
Senyawa Kompleks
Ion logam : sebagai inti (pusat)
Air alamiah: Mg
2+
, Ca
2+
, Fe
2+
, Fe
3+
, Cu
2+
, Zn
2+
, VO
2+

Ligan: donor pasangan elektron bebas (basa Lewis) dapat
bebentuk molekul, ion positif atau ion negatif. Gugus fungsi
dapat berupa:
O
-
R C
O
C
O
-
H
R N:
H
O
-
O P
O
O
R
Unidentat: membentuk satu ikatan koordinasi
Khelat : dapat membentuk lebih dari satu ikatan koordinasi

SUMBER:
ALAMIAH:Asam sitrat, Humus, Asam amino
SINTETIK: Polifosfat, EDTA, NTA
PENGARUH LIGAN TERHADAP LOGAM:
Menentukan bilangan oksidasi logam
Memnentukan tosisitas logam
Mempengaruhi logam terlarut
REAKSI ANTAR LIGAN:
Redoks
Hidrolisis
Dekarboksilasi

Perhitungan spesi senyawa kompleks
Kestabilan senyawa kompleks tergantung pada
konstanta pembentukannya:
Konstanta pembentukan pertahap, K
n
Konstanta pembentukan total (overall), |
n
|
n
=K
1
K
2
K
3
K
n
Zn
2+
+ NH
3
Zn(NH
3
)
2+
( )
| || |
3
2
2
3
1
NH Zn
NH Zn
K
+
+
=
Zn(NH
3
)
2+
+ NH
3
Zn(NH
3
)
2
2+

( )
( ) | |
3
2
3
2
2 3
2
NH NH Zn
NH Zn
K
+
+
=
|
2
= K
2
K
1

Pelarutan Ion Logam oleh NTA
Pb(OH)
2
(s) + HT
2-
PbT
-
+ OH
-
+ H
2
O
w
f a sp
K
K K K
HT
OH PbT
K
3
2
=
=

| |
2 a
f 3 a sp
2
3
K
K K K
HT
HCO PbT
K
'
=
PbCO
3
(s) + HT
2-
PbT
-
+ HCO
3
-
K
sp
= Hasil kali kelarutan
K
a3
= Konstanta kesetimbangan deprotonasi H
3
T tahap 3
K
w
= Konstanta ionisasi air
K
`
a2
= Konstanta kesetimbangan deprotonasi H
3
CO
3
tahap 2
Suatu limbah mengandung kalsium, timbal karbonat dan
NTA, hitung nisbah PbT/CaT yang terlarut!

Polifosfat
Sumber
Mineral fosfat
Pertanian
Pemukiman
Industri
Pengisi detergen
Kegunaan
Pelunakan air
Pengolahan air
Pengisi detergen
Polifosfat sederhana adalah Asam pirofosfat (difosfat )
Polifosfat merupakan pengkomplek yang baik untuk
ion logam alkali
Hidrolisis polifosfat menghasilkan asam fosfat
(ortofosfat)

Humus
Bahan kimia sisa penguraian tumbuhan, terdapat dalam
tanah, gambut dan batubara
Pengelompokkan
Humus
Endapan
(Humin)
Larutan
Endapan
asam humat
Larutan
asam fulfat
+ basa kuat
+ asam kuat

KESETIMBANGAN REDOKS
STUM DAN MORGAN | |
| || |
| |
| |
| |
| | OX
RED
log np np
OX
RED
log ] e log[ n K log
e OX
RED
K
o
e
n e
c = c
+ =
=
Pada Kesetimbangan, 25
o
C
Nerst : Log K = 16,92 E
o
Stum-Morgan: log K = npc
o
Hubungan pe
o
dengan E
o
npc
o
= 16,92 E
o

Redoks : Ox + ne Red
] Ox [
] d [Re
log
NF
RT 303 , 2
E E
O
=
PERSAMAAN NERST

Batas pc dalam air
pc tertinggi:
Suasana air paling oksidatif
Proton teroksidasi H
+
+ 1/4 O
2
+e 1/2 H
2
O E
o
= 1,229
pc
o
= 16,92 E
o
= 20,75
pc = pc
o
+log[H
+
] [P
O2
]
1/4
Bila P
O2
= 1atm, [H
+
] = 1M : pc = pc
o
= 20,75

Bila P
O2
= 1atm, [H
+
] =? : Pc = 20,75 pH
pc terendah:
Suasana air paling reduktif
Proton tereduksi
H
+
+ e 1/2 H
2
E
o
= 0, pc
o
= 0
Bila P
H2
= 1atm, [H
+
] =?
Pc = - pH

pE-pH Diagrams
ALLOWED CONDITIONS
IN THE PRESENCE OF LIQUID WATER
AT 1 ATM TOTAL PRESSURE
20
15
10
5
0
-5
-10
2 3 4 5 6 7 8 9 10
pE
pH
FORBIDDEN ZONE
FORBIDDEN ZONE
H
2
O
O
2

H
2
O
H
2


The Stability of Water and the pe- and pH-conditions in Natural Environments

-14
-12
-10
-8
-6
-4
-2
0
2
4
6
8
10
12
14
16
18
20
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
Batas atas
A
B
C
D
E
Batas bawah
Fe
3+
Fe
2+
Fe(OH)
3
Fe(OH)
2
O
2
H
2
Diagram pe vs pH Sistem Besi dalam Air


pe-pH stability in the
Fe-H
2
O-CO
2
system

at 25
o
C and
TIC = 10
-2.5
mol/l

C
2
HO

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