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Dasar-dasar Reaksi dan Sifat

Kimia Alam
Ranno Marlany Rachman
Hubungan
antar sistem
lingkungan
dengan
manusia dan
kehidupan
Environmental
Chemistry

• Is the study of the


sources, reactions,
transport, effects, and
fates of chemical
species in water, soil,
air, and living
environments, and the
effects of technology
thereon
Pertukaran Zat/Materi antar sphere
Carbon Cycle (1)
Siklus Karbon (C-Cycle)
Nitrogen cycle (2)
Siklus Nitrogen (N-cycle)
Sulfur Cycle
Siklus
Sulfur
(S-cycle)
Phosphorus cycle
Siklus Fosfat (P-cycle)
Beberapa impact teknologi pada
lingkungan
• Agricultural  perubahan lahan, drainase, irigasi,
pestisida
• Manufacturing  polusi udara, polusi air, by-
produk limbah hazard dsb
• Extraksi and produksi mineral  kerusakan
lingkungan dan polusi
• Produksi Energi dan penggunaannya 
kerusakan lahan/tanah, polusi air (garam), emisi
polutan udara (hujan asam) dsb
• Transportasi Modern automobile, perubahan
struktur tanah (jalan), emisi polusi udara,
peningkatan penambangan minyak dsb
technology can be applied to minimize
environmental impact

• maximum energy efficiency, maximum


utilization of raw materials, and minimum
production of pollutant by-products
• minimize pollution problems
• maximum materials recycling and minimum
waste product production
• advanced biotechnologies
• catalysts for efficient synthesis
• minimize waste production
Dasar-dasar Reaksi dan Sifat
Kimia Alam
Reaksi-reaksi Kimia
Air
Sanitation Condition
• Kurang dari 1% air siap pakai di dunia yang
layak digunakan.

• 10 negara pengguna air terbesar : India, China,


AS, Pakistan, Jepang, Thailand, Indonesia,
Bangladesh, Meksiko dan Rusia

• 20% penggunaan air secara global bersumber


dari air bawah tanah.
1.1
• Pada tahun 2030, 47% penduduk dunia hidup
dalam kelangkaan air

• Kebutuhan air sehari hari adalah 20-50


liter/org/hari yang bebas dari kontaminasi

• 87% populasi dunia-5,7 miliar minum dari air


olahan
• 2,5 miliar orang hidup dalam sanitasi yang
buruk
1.2
• Global warming - menyebabkan 2 miliar orang
terkena dampak bencana dan 86% akibat
banjir dan kekeringan

• Kenaikan suhu 3-4 0 C  300 orang


mengungsi akibat bencana ini.
Steady State
Addition and Removal
Siklus Air
(hydrolog
ic cycle)

dalam triliun
liter/hari
Air
• Struktur terdiri atas 2 atom H
dan 1 atom O dalam setiap
molekulnya
• Struktur bersudut 105 o 
moment dipol tidak nol (polar)
• Kemampuan sangat besar
membentuk ikatan hidrogen
(kelarutan molekul, logam,
suspensi)
• Pelarut yang universal
• Kapasitas panas tinggi
• Densitas terbesar pada 4 oC
(jaminan kelangsungan hidup)
Ikatan Hidrogen

26
Water Chemistry
The polarity of water causes it to be cohesive and
adhesive.
Polarity unequal charge distribution in a molecule resulting in a –
region and a + region
cohesion: water molecules stick to other water
molecules by hydrogen bonding
adhesion: water molecules stick to other polar
molecules by hydrogen bonding

27
Water Chemistry

cohesion
28
Water Chemistry

adhesion 29
Sifat
Air
Stratifikasi Air danau
Major Aquatic Chemical Process
Kesetimbangan CO2-CaCO3 di air
CO2 di Air
Kesetimbangan CO2 di Air
Oksidasi-Reduksi di Air
Properties of Water
1. Water has a high specific heat.
- A large amount of energy is required to change
the temperature of water.

2. Water has a high heat of vaporization.


- The evaporation of water from a surface causes
cooling of that surface.

37
Properties of Water
3. Solid water is less dense than liquid water.
- Bodies of water freeze from the top down.

38
39
Properties of Water
4. Water is a good solvent.
- Water dissolves
polar molecules and
ions.

40
Properties of Water
5. Water organizes nonpolar molecules.
- hydrophilic: “water-loving”
-hydrophobic: “water-fearing”
- Water causes hydrophobic molecules to
aggregate or assume specific shapes.

6. Water can form ions.


H2O  OH-1 + H+1
hydroxide ion hydrogen ion

41
Ionization; happens spontaneously
KELOMPOK

1. Berdasarkan properties of water, jika temperature di


dalam air naik, maka bagaimana dengan kelarutan
oksigen di dalam air ? (NAIK atau TURUN)

2. Sebutkan reaksi-reaksi kimia di dalam air ? Jika suhu


naik dalam air, maka bagaimana dengan kecepatan
proses tersebut? (MENINGKAT atau MELAMBAT)

3. Dalam siklus biogeokimia, decomposer berfungsi untuk


mendekomposisi bahan organik. Jika suhu naik dalam
air, maka bagaimana dengan pertumbuhan atau
perkembang biakan decomposer tersebut?
(MENINGKAT atau MELAMBAT)
STANDAR BAKU MUTU

AIR BERSIH atau AIR MINUM

Fisik Kimia Biologi


• Suhu • pH • E Coli
• Kekeruhan • DO • Total
• Conductivity • BOD Coliform
Syarat Air Minum
No Parameter Satuan Hasil Analisa Metode Analisa
*)
A. FISIKA
1 Bau - - -
2 Total Disolved Solid (TDS) mg/L 500 Gravimetri
3 Kekeruhan Skala NTU 5 Turbidimetri
4 Rasa - - -
o
5 Suhu C Suhu Udara Termometer
6 Warna Unit PtCo 15 Spektrofotometri
7 Daya Hantar Listrik (DHL) mmhos/cm - Conductivity meter
B. KIMIA
a. Kimia Anorganik
1 Air Raksa mg/L Hg 0.001
2 Aluminium mg/L Al 0.2 AAS
3 Ammoniak mg/L NH3 -N 1.5 Spektrofotometri
4 Arsen mg/L As 0.01 AAS
5 Barium mg/L Ba 0.7 AAS
6 Besi mg/L Fe 0.3 Spektrofotometri
7 Boron mg/L B 0.5
8 Fluorida mg/L F 1.5 Spektrofotometri
9 Kadmium mg/L Cd 0.003 AAS
10 Kesadahan Total mg/L CaCO3 500 Tetrimetri
11 Khlorida mg/L Cl 250 Argentometri
6+
12 Kromium, Valensi 6 mg/L Cr 0.05 AAS
13 Mangan mg/L Mn 0.4 Spektrofotometri
14 Natrium mg/L Na 200 AAS
15 Nikel mg/l Ni 0.07 AAS
16 Nitrat mg/L NO3 -N 50 Spektrofotometri
17 Nitrit mg/L NO2 -N 3 Spektrofotometri
18 Perak mg/L Ag 0.001 AAS
19 pH - 6,5 - 8,5 pHmeter
20 Selenium mg/L Se 0.01
7 Seng mg/L Zn 3 AAS
22 Sianida mg/L CN 0.07 Spektrofotometri
23 Sulfat mg/L SO4 250 Spektrofotometri
24 Sulfida mg/L H2 S 0.05 Iodimetri
25 Tembaga mg/L Cu 2
26 Timbal mg/L Pb 0.05 AAS
27 Sisa Khlor mg/L Cl2 5 Iodimetri
b. Kimia Organik
1 Zat Organik mg/L KMnO4 10 Oksidasi/Titrimetri
2 Detergent mg/L LAS 0.05 Spektrofotometri
C. BAKTERIOLOGI
1 Total Koliform MPN/100 mL 0 Fermentasi Multi Tabung
2 E. Coli MPN/100 mL 0 Fermentasi Multi Tabung
*) : Per. Men.Kes. No.: 492/Menkes/Per/IV/2010 Tanggal 19 April 2010
AIR LIMBAH  Efluent Standar

No Parameter Satuan Baku Mutu Hasil Metode


Air Limbah Analisa Analisa
Domestik *)

1 pH - 6-9 pHmeter
2 TSS mg/L 100 Gravimetri
3 BOD mg/L O2 100 Winkler
4 Minyak & mg/L 10 Gravimetri
Lemak
AIR PERMUKAAN  Stream Standar
Baku Mutu Air
No Parameter Satuan Hasil Analisa Metoda Analisa
Kelas I *)
A. FISIKA
o
1 Temperatur C deviasi 3 Termometer
2 Total Disolved Solid (TDS) mg/L 1000 Gravimetri
3 Padatan Tersuspensi (SS) mg/L 50 Gravimetri
B. KIMIA
1 pH - 6,0 - 9,0 pH meter
2 Barium mg/L Ba 1 AAS
3 Besi mg/L Fe 0.3 Spektropotometri
4 Boron mg/L B 1 AAS
5 Mangan mg/L Mn 0.1 Spektropotometri
6 Tembaga mg/L Cu 0.02 AAS
7 Seng mg/L Zn 0.05 AAS
6+
8 Krom Heksavalen mg/L Cr 0.05 AAS
9 Kadmium mg/L Cd 0.01 AAS
10 Raksa mg/L Hg 0.001 AAS
11 Timbal mg/L Pb 0.03 AAS
12 Arsen mg/L As 0.05 AAS
13 Selenium mg/L Se 0.0 AAS
14 Kobalt mg/L Co 0.2 AAS
15 Khlorida mg/L Cl - Argentometri
16 Sulfat mg/L SO4 400 Spektropotometri
17 Sianida mg/L CN 0.02 Spektropotometri
18 Sulfida mg/L H2S 0.002 Iodometri
19 Fluorida mg/L F 0.5 Spektropotometri
20 Sisa Khlor Bebas mg/L Cl2 0.03 Iodometri
21 Total Phospat mg/L PO4 -P 0.2 Spektropotometri
22 Nitrat mg/L NO3 -N 10 Spektropotometri
23 Nitrit mg/L NO2 -N 0.06 Spektropotometri
24 Amonia Bebas mg/L NH3-N 0.5 Spektropotometri
25 BOD mg/L O2 2 Winkler
26 COD mg/L O2 10 Reflux/Titrimetri
27 Disolved Oxygen (DO) mg/L O2 6 Iodometri
28 Detergent Anionik mg/L LAS 0.2 Spektropotometri
29 Fenol mg/L 0.001 Spektropotometri
30 Minyak & Lemak mg/L 1 Gravimetri

*) = PP. No. 82 Tahun 2001 Tanggal 14 Desember 2001


Baku Mutu Air Laut
SAMPLE REGULATORY
NO. TEST DESCRIPTION UNIT METHOD
RESULT LIMIT*
I. Physical Properties
1 Odour Odourles s - Odor SNI 06-6860-2002
Total Sus pended Solids ,
2 50 80 m g/L SNI 06-6989.3-2004
TSS
3 Was te - Nihil -
4 Tem perature 29 Air Tem p. ± 3 oC SNI 06-6989.23-2005
II. Chemical Properties
5 pH 7.43 6.5 - 8.5 - SNI 06-6989.11-2004
6 Salinity (NaCl) 25.3 Nature 0%
7 Free Am m onium , NH3-N <0.01 0.3 m g/L SNI 06-6986.30-2005
8 Sulfida,H2S 3 0.03 m g/L SNI 6989.70-2009
9 Phenol <0.005 0.002 m g/L SNI 06-6989.21-2004
10 Surfactants , MBAS <0.025 1 m g/L SNI 06-6989.51-2005
11 Oil and Greas e <2.7 5 m g/L SNI 06-6989.10-2004
III. Dissolved Metal
12 Mercury, Hg** <0.000002 0.003 m g/L APHA 3112 B-2005
13 Cadm ium , Cd 0.176 0.01 m g/L SNI 6989.16-2009
14 Tem baga,Cu <0.0014 0.05 m g/L SNI 6989.6-2009
15 Lead, Pb 0.2 0.05 m g/L SNI 6989.8-2009
16 Zinc, Zn 0.125 0.1 m g/L SNI 06-6989.7-2004
III. Biology
Total Coliform (Mem brane
17 <1 1000 MPN/100m l APHA 9222 B-2005
Filter)**
Sumber: Hasil Monitoring Lingkungan KLHS KKJSS, 27 Juni 2012
Per MenLH No. 52 Tahun 2004
KONDISI KUALITAS AIR TANAH
(sumber : Survey Kualitas Lingkungan [air, udara dan laut])
KONDISI KUALITAS AIR PERMUKAAN
(sumber : Survey Kualitas Lingkungan [air, udara dan laut])
PLANKTON & BENTHOS PERAIRAN LAUT
(sumber : Survey Kualitas Lingkungan [air, udara dan laut])

Pseudo- Larva naupulius Larva


Skeletonema Thalassionema
nitzchia Nitzchioides cirripedia Brachyura

Menunjukkan kadar nutrient di Produktivitas laut tinggi


laut sangat tinggi seperti dan tidak ada
konsentrasi nitrogen dan pencemaran akibat
phosphat pestisida
PENCEMARAN DARI AIR
PERMUKAAN
Water Quality Parameters
Temperature - Dissolved Oxygen (DO) - pH
Alkalinity - Hardness
Nitrates and Phosphates - Turbidity
Conductivity
-
Temperature
Affects:
Water density
The solubility
Chemical reaction rates
Organism growth rates
Conductivity
pH
Dissolved Oxygen
Contoh : Jika CuO, di dalam air dengan suhu 250C
mempunyai log Kso = 10 7.644 dan entalphy adalah -15.504
kcal/mol atau – 64.90 kJ/mol. Berapa solubility dari CuO
jika temperature di dalam air turun 10oC
TEMPERATURE NAIK, SOLUBILITY AKAN
MENURUN DAN VISE VERSA
Q10 rule
cold-blooded aquatic organisms

Predicts that growth rate will double


if temperature increases by 10˚C
(18˚F) within their "preferred" range.
Gases Dissolve in Water
Oksigen di Air
• O2 dibutuhkan terlarut di air untuk menjaga
reaksi oksidasi-reduksi, respirasi, degradasi dst
• Kelarutan O2 di air tergantung temperatur, pd
25 oC  sekitar 8,5 mg/L; pada 0oC  14,74
mg/L

• Dihasilkan dari proses fotosintesis


alga/tumbuhan hijau di air dan proses aerasi
Henry’s Law

Henry’s Law Constant

For example, oxygen is 20.95% of the


air on a molar basis and, therefore, PO2 is
20.95% of the atmospheric pressure,
or 0.2095 atm under standard conditions.]
BAGAIMANA KELARUTAN OKSIGEN
JIKA TEMPERATURE NAIK ?

Suhu 15oC dan 20oC


Dissolved Oxygen (DO)
DO is the measurement of oxygen
dissolved in water and available for
fish and other aquatic life.

Indicates health of an aquatic system.

Can range from 0-18 ppm.

Most natural water systems require 5-


6 ppm to support a diverse population.

Varies with time of day, weather, temperature.


Dissolved Oxygen (DO)
Increase in organic waste

Increase in algae/plant vegetation

Decrease in DO available to organisms

Leads to changes in ecosystem as


organisms needing lots of DO are
replaced by organisms needing little.
Self Purification
pH - p(otential of) H(ydrogen)

Determines the solubility of nutrients (PO4-3, NO3-, C)


and heavy metals (Fe, Cu, etc)

Determines availability of these chemicals for use by aquatic life.

In natural water systems, determined largely by geology and soils.


pH of natural waters

Limestone, marble, CO3 rich


due to humic acid

Sea water

Pure rain, snow


Factors that affect pH
• Algal blooms
• Bacterial activity
• Water turbulence
• Chemicals flowing into the water body
• Sewage overflows
• Pollution
How pH affects aquatic life
Decreasing pH
(e.g.: via acid rain)

Liberation of Al, metals

Toxic conditions

Chronic stress

Smaller, weaker fish
Alkalinity refers to the capability of water to neutralize acid.

Alkalinity
Buffering capacity –
resistance to pH changes.

Common natural buffer: CO3


(carbonates – like
limestone).

Protects aquatic life.

Commonly linked to water


hardness.

In natural systems:
Limestone outcrop 50 – 150 mg/L as CaCO3.
Hardness
Reflects dissolved
carbonate minerals.

Mostly of concern for


drinking water
standards.

Metals precipitate out


of solution.

Create scale/hard
water deposits

High alkalinity  Hard


water
and
Nitrate (NO3-)
Phosphate (PO4-3)
naturally-occurring
naturally occurs in
form of nitrogen
rocks and minerals.
found in soil.
Plants uptake
Forms by microbial
weathered-out
decomposition of
elements and
fertilizers, plants,
compounds.
manures or other
organic residues
Animals ingest plants.
Plants uptake
Water soluble.
nitrates (Spinach a
good source).

Redfield Ratio: 106:16:1


Artificial sources:
• Livestock
manure/urine
Nitrates • Failing septic
systems
• Synthetic fertilizers

Can lead to:


eutrophication of natural
water systems
(overproduction of
vegetation)

Blue baby syndromne


The U.S. EPA has set a maximum
contaminant level for NO3- in drinking
water of 10 parts per million (ppm)
Phosphates
Artificial sources:
• Sewage
• Laundry,
cleaning fluids
• Synthetic
fertilizers

Can also lead to


eutrophication of
natural water
systems
(overproduction of
vegetation)

Blue green algae


1990 and 1999 comparison
of Nitrates in Great Lakes

From US EPA
http://www.epa.gov/glnpo/monitoring/limnology/SprNOx.html
Solutions??

Wetland restoration Reduce fertilizers

Reduce soil erosion


Reduce emissions – WWTP/industry
Turbidity

Measures how
“murky” the water is

Estimates:

Mineral fraction
Organics
Inorganics
Soluble organic compounds
Plankton
Microscopic organisms

MODIS Image from NASA


http://rapidfire.sci.gsfc.nasa.gov/
Causes of highly waters

• In open waters, phytoplankton


• Closer to shore, particulates
Resuspended bottom
sediments (wind)
• Organic from stream and/or
wastewater discharges.
• Channelization
• Increased flow rates
• Too many bottom-feeding fish
(such as carp)
Effects of highly waters

• Modify light penetration


• Increase sedimentation rate
• Smother benthic habitats
• Settling clay particles
• Fine particulate material also can
damage sensitive structures
• Decrease organism resistance to disease
• Prevent proper egg and larval development
• Macrophyte growth may be decreased
• Reduced photosynthesis can lead to lower daytime release of oxygen
Conductivity
Ability of a substance to conduct an electrical current.

Cl- In water, conductivity determined by types and quantities of dissolved


solids. (Commonly called Total Dissolved Solids = TDS)

Current carried by ions (negatively or


positively charged particles).
Cl- Cl- Cl- Cl-
Na+
Na+ Na+ Na+ Na+
Eg: NaCl(aq) = Na + + Cl –
Cl- Cl- Cl- Cl-
Cl- Na+ Na+ Na+ Na+

Cl- Cl- Cl- Cl-


Cl- Na+ Na+ Na+ Na+ Na+

Na+ Cl- Cl- Cl- Cl-


Na+ Cl- Na+ Na+ Na+ Na+
Na+
Cl-
Conductivity
Conductivity of natural waters depends upon:

Ion characteristics (mobility, valence, concentration)


Water temperature
Geology
Size of watershed
Evaporation

Some artificial factors that can affect conductivity:


Wastewater
Urban runoff (especially road salt)
Agricultural runoff
The Components of Salinity

The most abundant components


of a kilogram of seawater.

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