Beruflich Dokumente
Kultur Dokumente
and
Prevention
Introduction to Water Chemistry
y
Atomic Structure
10 P Valence Shell
1 Covalent Compounds
1.
2. Ionic Compounds
Covalent Bonds
1P
8P
1P
Hδ+
Οδ¯
Hδ+
Na+ Cl ¯
11 P 17 P
Na+ Cl¯
+ –
Ο δ¯ Na+ Cl ¯ Ο δ¯
Ο δ¯
Anodic Reaction:
M Æ Mn+ + n e-
where:
M = metal involved
n = valence of the corroding metal species
e = electrons
Ionization of Solid Metals
by oxidation at Anode
Fe++
Ο
Οδ¯
26 P
ΟΗ¯
Cathodic
Hδ+
Anodic Οδ¯
Hδ+
ΟΗ¯
Anodic Reaction
Ο δ¯ Ο δ¯
Ο δ¯ Fe2+
Fe2+
Aerated Water
O2
O2 O2 O2 O2
O2
O2 O2
O2 O2
O2 O2
Fe Æ Fe2+ + 2 e-
Cathodic Reaction
• Hydrogen evolution (acids):
2 H+ + 2 e- Æ H2
• Oxygen reduction (acids):
½ O2 + 2H+ + 2 e- Æ H2O
• Oxygen reduction (neutral or base):
½ O2 + H2O + 2 e- Æ 2 OH-
Fe++
Οδ¯
Ο
26 P
ΟΗ¯
Cathodic
Hδ+
Anodic
Οδ¯
Hδ+
ΟΗ¯
Corrosion
Electrochemical Cell
O2 Aerated Water
O2
O2 O2
O2
O2 O2 O2
O2 O2
O2
O2
δ+
Hδ+ δ+
δ+δ+
HH Hδ+ Hδ+ Hδ+ Hδ+ HHδ+δ+Hδ+ HHδ+δ+ Hδ+ Hδ+ Hδ+ H
H
H
δ+
δ+
Hδ+
δ+ H
Hδ+
H δ+
δ+
+ Anode +
OH
OH
OH - - OH
OHOH --OH
-- -
O
OOHO
OH
22 2O O
O222
-- -
OOO22OH
2 OO 2 OOH
δ- -O OH
δ-
2
--
O2OHO
- δ-
O2OH
OO2OH
- δ-- - δ-
OH
2O O Oδ-OOH 2
-- δ- OH
OH-O - -
OH O2OHO 2
O
- δ- O OH
OH
δ-
δ-
Oδ- ---
2 O O222
e- - Fe2+ e-- e-
ee-
-
- Cathode - Fe2+
e Fe
e-e-
Fe
2+ 2+ e2+ e-
Fe Fe2+
e
2+- Fe2+
- - Cathode -
Fee e-
e -
- Fe 2+
Fee2+
-
e e-
e-
Precipitates:
Fe3+ + 3OH Æ Fe(OH)3 Ferric Hydroxide
Oxidation of Dissolved Iron
OH- O2
Fe3+
OH- OH- O2
OH- O2
O2 Fe3+
OH- O2 O2
Fe3+ OH-
OH-
OH- -
OH OH Fe3+
- A
Aerated
t d Water
W t O2
OH-
Fe3+
O2 OH- OH- - 3+ OH- O2
OH- Fe
OH
OH- OH- OH- OH-
O2 Fe3+ OH-
Fe Fe
3+ 3+ OH -
OH- O2
OH- OH- FeOH
3+ -
O2 OH- OH-
O2
O2 OH- O2
OH-
O2 O2
O2 O2
O2
O2
O2
O2
O2 O2
O2
O2
O2
O2
O2
Hδ+ HH H
δ+δ+δ+ δ+ δ+δ+ δ+
H HH H Hδ+ Hδ+ Hδ+Hδ+ Hδ+Hδ+ HHδ+δ+ Hδ+HHδ+δ+ Hδ+
OH - O-2δ-δ-
- - δ-
OOH
OH - - - - - OH- - -δ-- - OH- -OH --
OO
O OH
OH
OO2OOH OO OHOH
O22OOH OH O OHOHO
OH OH OH
OH O- δ-
O OH
2 2 OO2 2O2 O
- -OH
OHO2OH
OH - - OH
- O
OOH
- δ-
OH -OH
OH - δ-- -
2O2 OO2
δ-
222 O 22O2O δ-
2 OO2 2 2 O O 22 O22O 2O
δ-
ee
- -
e-2+- e- - 2+ e- - Fe 3+ ee
--
eFe
Fe- 2+
3+
e Fe
- Fe
Fe2+ e
3+Fe
Fe 3+ e Fe
Fe Fe
3+ 2+ e Fe2+
Fe2+
3+ Fe3+ 2+
ee- - Fe
Fe2+
3+ e-
Fe 3+
- Fee-
Fe
Fe ee
2+
3+
-
e-e-
Formation of Passive Layer at Cathode
Fe2+ + 2OH- Æ Fe(OH)2 (Ferrous Hydroxide)
( )2((s)) + O2(g) Æ 4H2O(l)
6Fe(OH) ( ) + 2Fe3O4.H2O(s)
( )
Green Hydrated Magnetite
Fe3O4.H2O Æ H2O + Fe3O4 Black Magnetite
g (passive
(p layer)
y )
4Fe(OH)2 + O2 + 2H2O Æ 4Fe(OH)3 (Ferric Hydroxide)
Fe(OH)3 Æ FeO(OH).
FeO(OH) H2O Æ FeO(OH) + H2O
2FeO(OH) Æ Fe2O3.H2O Hydrated Ferric Oxide
( d Brown Rust))
(Red
Fe2O3.H2O Æ Fe2O3+ 2H2O (alpha
(alpha or gamma)
gamma)
Formation of Passive Layer at Cathode
• General corrosion
• Galvanic Corrosion
• Concentration Cell Corrosion
• Dealloying
• Erosion Corrosion
• Microbiologically
c ob o og ca y Influenced
ue ced Co
Corrosion
os o
General Corrosion
Aerated Water
O2
O2 O2 O2 O2
O2
O2 O2
O2 O2
O2 O2
+- Anode
Cathode+- -+Cathode
Anode +- e- - Fe2+
- Cathode
+ Anode- +
e-- e-- 2+ ee-
2 Fe 2 -
F 2+
e- - Fe2+ - -
e- e e- -
Fe2+ e- - Fe2+ e-- e e2+ e Fe
ee-Fe2+
- e- -
e e2+ e-Fe2+ e e e2+ Fe2+
e Fe2+
Fe e -
e-eFe
2+
Fe2+Fe Fe2+ Fe
e-eFe
2+
e-
Fe2+- e- Fe2+ e- - 2+- Fee-
Fee
2+
- Fee
2+- e e- 2+- Fee-
Fee
2+
e-
e-
e-
Fe Æ Fe2+ + 2 e-
General Corrosion
Galvanic Corrosion
O2 Aerated Water
O2
O2 O2
O2
O2 O2 O2
O2 O2
O2
O2
+ Anode +
Zinc
δ+
Hδ+ HH δ+
δ+δ+
Hδ+ Hδ+ Hδ+ Hδ+ HHδ+δ+Hδ+ HHδ+δ+ Hδ+ Hδ+ Hδ+ H
H
H
δ+
δ+
Hδ+
δ+ H
Hδ+
H δ+
δ+
OH
OH
OH - - OH
OHOH --OH
-- -
O
OOHO
OH
22 2O O
O222
-- -
OOO22OH
2 OO 2 OOH
δ- -O OH
δ-
2
--
O2OHO - δ-
O2OH
OO2OH
- δ-- - δ-
OH
2O O Oδ-OOH 2
-- δ- OH
OH-O - -
OH O2OHO 2
O
- δ- O OH
OH
δ-
δ-
Oδ- ---
2 O O222
e- - Zn2+ e-- e-
ee-
-
- Cathode - Zn2+
e Zn
e-e-
Zn
2+ 2+ e2+ e-
Zn Zn2+
e
2+- Zn2+
- - Cathode -
Zne e-
e -- Zn 2+
Zne2+-
-
Steel e e
e- Steel
• Concentration
Concentration--cell corrosion occurs because
of differences in the environment surrounding
the metal.
• This
Thi form
f off corrosion
i commonly
l occurs in
i
localized areas where small volumes of
stagnant solution exist.
exist
• Normal mechanical construction can create
crevices
i att sharp
h corners, spott welds,
ld joints,
j i t
fasteners, flanged fittings, couplings,
threaded joints,
joints etc
etc…
Concentration Cell Corrosion
O2 O2
O2
Aerated Water
O2
O2
O2 O2
O2
O2
O2 O2
O2
O2
O2
δ+ δ+ Hδ+
Hδ+ δ+δ+
HH Hδ+ Hδ+
OH
OH-- - OH-- δ- - δ- - -
OH OO22OH
2 O OOH
O22 O OOHOH
2 O2OHO - δ-
e- - 2+ e-
eFe Fe e-2+
e - Fe2+
-
e
e-- 2+
eFe
O2
O2 Aerated Water
O2 O2
O2
O2
O2 O2
O2 O2
P
Passive
OH- i Layer
L
OH- OH- OH- OH- OH-
Hδ+ Hδ+ Hδ+ Hδ+
OH- OH- OHOH
-
P OH
Passive
-
i Layer
-
LOH -
- Oδ-OHO
-
OH- OH-
Oδ- Oe2 - e
Fe --
2+ 2
e- Fe
2+
e
OH
- Cathode - +e-Anode
Fe
+ 2+
- Cathode -
e-
Fe2+ e-
e-
eFe- 2+
e-
Fe2+ e-
e-
eFe
-
2+
e-
Fe2+
e--
e
eFe-
2+
e- 2+ e-
Fe
- 2+ e
-
eFe
e 2+ e-
-
Fe
eFe- 2+ e-
eFe- 2+ e-
- 2+ e
-
eFe
e -
Fe2+ e-
-
e
O2
O2 Aerated Water
O2 O2
O2
O2
O2 O2
O2 O2 O2
- Cathode - OH-
- Cathode -
Fe2+
H+ OH-
H+
2+ OH
-
OH
Fe
-
H+ Fe
2+
H+
Fe2+
OH-
Fe2+
OH-
H+
H+
Fe2+
O2
O2
O2 O2
O2
O2
O2
C Fe C Fe C Fe C Fe
Fe++ e-
e- C Fe C Fe C Fe C Fe
Fe C Fe C Fe C Fe C Fe
Fe++ e-C Fe C Fe C Fe C
e-
C Fe C Fe C Fe C e-Fe++
Fe C Fe C Fe C Fe C Fe
e-
Fe C Fe C Fe C Fe C Fe
Fe++ e-C Fe C Fe C Fe C
e-
Erosion Corrosion
• Erosion corrosion refers to the repetitive formation
and destruction of a metal
metal'ss protective surface film.
This typically occurs in a moving liquid.
• The formation of a protective film can be due to the
cathodic process which creates an oxide layer on
the p
pipe
p surface.
• The destruction of the protective film is mechanical
due to high
g velocityy flow of water,, especially
p y if it
contains suspended solids.
• Erosion corrosion often occurs in copper heat
exchanger tubes.
Erosion-Corrosion Process
O2
Aerated Water
O2
O2 O2
O2
O2
O2
O2
O2
O2 O2
O2
Passive Film
Base Metal
Microbiologically Influenced Corrosion
• Iron
Iron--oxidizing bacteria are aerobic bacteria
which oxidize ferrous ions to less soluble ferric
ions.
ions.
Fe2+ Æ Fe3+ + e-
• The resulting ferric ions precipitate as ferric
hydroxides forming tubercules in the pipes.
Oxidation of Dissolved Iron
OH- O2
Fe3+
OH- OH- O2
OH- O2
O2 Fe3+
OH- O2 O2
Fe3+ OH-
OH-
OH- -
OH OH Fe3+
- A
Aerated
t d Water
W t O2
OH-
Fe3+
O2 OH- OH- - 3+ OH- O2
OH- Fe
OH
OH- OH- OH- OH-
O2 Fe3+ OH-
Fe Fe
3+ 3+ OH -
OH- O2
OH- OH- FeOH
3+ -
O2 OH- OH-
O2
O2 OH- O2
OH-
O2 O2
O2 O2
O2
O2
O2
O2
O2 O2
O2
O2
O2
O2
O2
Hδ+ HH H
δ+δ+δ+ δ+ δ+δ+ δ+
H HH H Hδ+ Hδ+ Hδ+Hδ+ Hδ+Hδ+ HHδ+δ+ Hδ+HHδ+δ+ Hδ+
OH - O-2δ-δ-
- - δ-
OOH
OH - - - - - OH- - -δ-- - OH- -OH --
OO
O OH
OH
OO2OOH OO OHOH
O22OOH OH O OHOHO
OH OH OH
OH O- δ-
O OH
2 2 OO2 2O2 O
- -OH
OHO2OH
OH - - OH
- O
OOH
- δ-
OH -OH
OH - δ-- -
2O2 OO2
δ-
222 O 22O2O δ-
2 OO2 2 2 O O 22 O22O 2O
δ-
ee
- -
e-2+- e- - 2+ e- - Fe 3+ ee
--
eFe
Fe- 2+
3+
e Fe
- Fe
Fe2+ e
3+Fe
Fe 3+ e Fe
Fe Fe
3+ 2+ e Fe2+
Fe2+
3+ Fe3+ 2+
ee- - Fe
Fe2+
3+ e-
Fe 3+
- Fee-
Fe
Fe ee
2+
3+
-
e-e-
Microbiologically Influenced Corrosion
Effects of Biofilms on Corrosion
• Some types of aerobic bacteria form protective
biofilms (slime).
(slime)
• The aerobic bacteria consume the oxygen in
the outer layer
y of the biofilm leavingg an oxygen
yg
free environment that allows anaerobic
bacteria to thrive.
• The difference between dissolved oxygen
concentration beneath the biofilm vs. outside
the biofilm creates an oxygen cell – the area
b
beneathth the
th biofilm
bi fil becomes
b the
th anode.
d
• The slime allows water and nutrients to enter
but can filter out certain toxic compounds that
are harmful to the bacteria.
Effects of Biofilms on Corrosion
Aerated Water
O2 O2
O2 O2 O2
O2
O2
O2
BIOFILM
O2 O2
O2 O2
O2 AerobicO2 O2
O2
O2
O2
O2 Anaerobic
O2
O2
O2
O2
O2
δ+
Hδ+ HH δ+
δ+δ+
Hδ+ Hδ+ Hδ+ O2 Anaerobic Hδ+ HHδ+δ+Hδ+ HHδ+δ+ Hδ+ Hδ+ Hδ+ H
H
H
δ+
δ+
Hδ+
δ+ H
H δ+
δ+
Hδ+
OH
OH
OH
-- - - - OH
OH
OH-- - --OH OH - δ- O2 -- δ- OH- -
O
OOHO
OH O O
O
22 2 222 OO O OH
222 OO 2 OOH
δ- -O OH
δ-
2
--
O2 O O2OH
OO2OH
- δ-- - δ-
OH
2O O Oδ-OOH OH-O
2
OH O2OHO 2
O
- δ- O OH
OH
δ-
δ-
Oδ- ---
2 O O222
e- - Fe2+ e-- e- - e- -
Fe2+
e e e Fe2+
Fe2+ Fe2+ e
Cathode Fe2+
e- - Cathode
e-e- Fee 2+- Fe2+
e
e- -
Fe2+
Fee2+
-
e e- -
e
Anode
Controlling Corrosion
Corrosion Problems
• Consumer
C complaints
l i t about
b t Red
R d Water
W t
• Compliance
p with EPA’s Lead and Copper
pp Rule
Degassifiers:: Effect on Alkalinity
Degassifiers
• Alkalinityy provides
p buffering
g capacity
p y in water systems
y
CO32- + H+ HCO3-
HCO3- + H+ H2CO3
• Buffering is the ability to minimize pH fluctuations
resulting from introduction of acids or bases
15 30 45 60 74
ppm ppm ppm ppm ppm
Alkalinity
pH – Effects on Corrosion
Lead
0.20
L)
n (mg/L
olved
0.15 0.128
fro m Corrrosion
Lead Disso
0.10
0.05 0.035
0 008
0.008 0.004
0.00
6.7 8.5 9.2 10.5
pH
Alkalinity – Effects on Corrosion
Copper
• Alkalinity
a y <25
5 mg/L
g/ as CaCO3 increases
as s
uniform corrosion of copper.
• However, copper corrosion also increases
when alkalinity is >74 ppm due to the
formation of soluble cupric bicarbonate and
carbonate
b t complexes
l – this
thi effect
ff t iis made
d
worse if the pH is also < 7.8
• At pH>8
H 8 copper corrosion
i that
th t occurs will
ill
be non-uniform or pitting corrosion.
Alkalinity – Effects on Corrosion
C opp er R eleease Copper
n W ate r
in
1
15 2
25 3
35 4
45 55 6
65 75 8
85 9
95
Alkalinity
Alkalinity – Effects on Corrosion
Copper
• Copper
pp is least soluble at pH>9.
p Chlorine
in water oxidizes copper surfaces to form a
protective passive
p p layer
y that prevents
p
further corrosion. This passive film will
dissolve if pH<9.
p
Alkalinity
30 45
Iron
Copper
Lead
15 25 35 45 55 65 75
Alkalinity
Corrosion Inhibitors
1. Anodic Inhibitors
Inhibitors:: Form a film on the anode
to prevent water from directly contacting the
metall surface
f
2. Cathodic Inhibitors:
Inhibitors: Form a precipitated
barrier at the cathode to reduce the flow of
electrons.
Anodic Corrosion Inhibitors
O2
PO43- PO43- O2 PO43-
O2 O2 PO43-
O2 O2
PO43-
PO43-
O2 PO43-
PO43- PO43-
PO43-
PO43- O2 O2
PO43- PO43- O2
O2 PO43- PO43- PO43- 3- PO43-
PO4 + Anode + PO43-
PO
PO43-
3-
PO4 43- O2
PO43-
PO43-
PO43- PO43- PO43-
O2 PO43- PO43- O2 PO43-
PO43-
O2
O2 Aerated Water
PO43- O2 O2 PO43-
O2 PO43-
PO43- O2
PO43- O2 O2
PO43-
O2 O2
OH- OH- OH- OH- OH- OH- Hδ+ Hδ+
OH- OH- OHOH
- - OH- OH-
Hδ+ Hδ+
- Oδ-OHO
-
OH- OH-
Oδ- Oe2 - e
Fe --
2+ 2
e- Fe
2+
e
OH
- Cathode - + - Cathode -
e- Anode
Fe2+ +
e-
Fe2+ e-
e-
eFe- 2+
e-
Fe2+ e-
e-
eFe
-
2+
e-
Fe2+
e--
e
eFe-
2+
e- 2+ e-
Fe
- 2+ e
-
eFe
e 2+ e-
-
Fe
eFe- 2+ e-
eFe- 2+ e-
- 2+ e
-
eFe
e -
Fe2+ e-
-
e
Anodic Corrosion Inhibitors
• Orthophosphate: Effective in distribution
systems at moderate dosages
• Silicate: Very effective but require extremely
high dosages
• Molybdate: The best of the anodic corrosion
inhibitors but high dosage and high cost
prevent its use for large scale systems
systems.
• Borate: Boron is a possible carcinogen so this
is only used in industrial systems.
• Nitrite: Nitrite is useful in oxygen free systems
such as chillerss bu
su but iss not
o us
used
d in drinking
d g
water systems.
Cathodic Corrosion Inhibitors
• Cathodic Corrosion Inhibitors work by
precipitating hydroxide, carbonate or phosphate
films at the cathode:
• Precipitation of these salt films occurs due to the
increased pH from hydroxyl ions produced by
reduction of oxygen
• These salt films are thick and sometimes visible
• The films formed at the cathode restrict diffusion
of dissolved oxygen to the metal surface
surface.
• The salt films are also poor electronic
conductors and so oxygen reduction does not
conductors,
occur on the film surface.
surface.
Cathodic Protection
Zn2+
Zn2+ Zn2+ Zn2+
O2 Aerated Water
O2
O2 O2 Zn2+ O2
Zn2+ Zn2+
Zn2+ Zn2+
O2
Zn2+ Zn2+
O2
Zn2+ Zn2+ O2 Zn2+
O2 O2 Zn2+
Zn2+ Zn2+ Zn2+ Zn2+
O2 Zn2+
Z 2+
Zn Zn2+ Z 2+
Zn Z 2+
Zn
Zn2+ Zn2+ Zn2+
Zn2+ Zn2+ Zn2+ Zn2+ Zn2+ Zn2+
Zn2+ Zn2+ 2+2+
ZnZn
Zn2+ Zn2+ 2+2+ Zn2+
Zn
Zn2+Zn Zn2+ Zn2+Zn
Zn 2+ 2+
Zn2+ O2
Zn2+ Zn2+ 2+ 2+
ZnZn
Zn2+
Zn2+ Zn2+
OH
OH- - -
OH OH
OH
OH
-- - OH- - -
OH
OH OH-- -
OH
OH OH
- --
OH
OH - - - OH
OH
OH
OH OH
OH
OH- - OH-- -
OH-OH
OH OH
-OH - - - OH
-OH OH-OH
-
OH
OH OH
- --OH-- - OH-
OH OH-
e- e
- e- - Fe2+ e- 2+ e--
e Fe e2+
- - e-
Fe2+ Feee
2+
Fe- 2+ Fe
e-ee-
Fe2+ e- - Cathode - e- -Fe2+
e
Zinc
• This is the most superior of the Cathodic Inhibitors
• The zinc works byy pprecipitating
p g as a zinc hydroxide
y
(Zn(OH)2) on the cathodic surface, inhibiting the
reductions.
Zinc
Zi corrosion
Zinc i inhibitors
i hibit provide
id substantial
b t ti l
protection of asbestos-cement pipe by
coating the pipe and protecting it against
fiber release and water attack.
Cathodic Corrosion Inhibitors
Calcium
• Traditionally believed to form a Calcium
Carbonate Film on the metal surface when
Calcium and Alkalinity concentrations are
sufficiently high. However, most studies show
that Calcium Carbonate by itself does not form
a protective scale on metals and is not an
effective corrosion inhibitor.
• Under certain conditions calcium has been
found to increase lead solubility
solubility.
Cathodic Corrosion Inhibitors
Magnesium
Forms a Magnesium Hydroxide Film on the
metal surface only when Magnesium
concentration is sufficientlyy high
g (Sea
( water).
)
Magnesium hydroxide films are only stable at
very high pH.
Cathodic Corrosion Inhibitors
Polyphosphates
yp p
• Will produce a thin, amorphous salt film ONLY in the
presence of Zinc or high levels of Calcium.
• When used alone, polyphosphate does not act towards
iron as a corrosion inhibitor but as a sequestrant, causing
a decrease in the visual observation of red water
water.
• If polyphosphate products are dosed in systems with
insufficient calcium and alkalinity
alkalinity, they will actually
increase the rate of corrosion of the steel pipe as they
sequester iron from the surface. However, since
polyphosphates
l h h decrease
d the
h appearance off red d water,
this corrosion goes unnoticed.
• Many studies have shown that polyphosphates will
increase corrosion of steel, copper and lead when used in
absence of zinc.
Anodic/Cathodic
Corrosion Inhibitors
45 Blank
Poly/Ortho
40
C o rro ssio n R atte (M P Y )
A-751
35
30
25
40.61
20
15
24.96
10
5 1.73
0
Mild Steel
Corrosion Coupon Tests
Port St. Lucie - JEA Plant
RO Water
6 Blank Poly/Ortho A-751
5.13
PY)
5
Rate (MP
3.91
4 3.56
osion R
3 2 73
2.73
2 1.68
Corro
1 40
1.40
1.13
1
0.18 0.12
0
Copper Brass Lead
Corrosion Coupon Tests
Port St. Lucie - Prineville Plant
RO Water Blended with Lime Softened Water
Corrosion Coupon Tests
Port St. Lucie - Prineville Plant
RO Water Blended with Lime Softened Water
25 Blank
Poly/Ortho
C o rro ssio n R atte (M P Y )
20 A-751
15
23.82 23.62
10
5
3 16
3.16
0
Mild Steel
Corrosion Coupon Tests
Port St. Lucie - Prineville Plant
RO Water Blended with Lime Softened Water
2.5 Blank Poly/Ortho A-751
2.16
PY)
20
2.0
Rate (MP
1.75
1.5
osion R
0.92 0.93
1.0 0.84
0.70
Corro
0 52
0.52
0.5 0.39
0.32
00
0.0
Copper Brass Lead
Water Quality for
p
Optimal Corrosion Inhibition
Perform
P f C
Corrosion
i C
Coupon studies
t di tto ensure
adequate corrosion control.
Ionic Bond
Fe++
26 P
Concentration Cell Corrosion