Bernard BubnisNovaCem Laboratories, Inc.
Oxford, OH USAwww.novachemlabs.com
Sponsored by: Powell Fabrication
Understanding Bleach Degradation
NovaChem Laboratories, Inc.
Testing bleach since 19891990’s - AWWA Bleach Decomposition
StudyCollaboration with Powell Fabrication &
ManufacturingDecomposition Model StudiesChemistry Validation Measurement Protocols for
◦Inorganic disinfection by-products◦Transition metal ions
Bleach Degradation
Parameters That Influence Decomposition◦Concentration◦Temperature◦Ionic Strength◦Transition Metal Ions
What is the chemistrythat controls decomposition
and the formation of disinfection by-products ?
Bleach Decomposition
2nd Order Rate = k2 [OCl-]2
Primary Pathway OCl- + OCl- → ClO2- + Cl-
OCl- + ClO2- → ClO3
- + Cl-
Stoichiometry 3OCl- → ClO3- + 2Cl-
Secondary Pathway OCl- + OCl- → O2 + 2Cl-
“uncatalyzed” and “catalyzed”
OCl- Lost …ClO3- Formed
Decomposition Comparison (90°F) Concentration Effect
0 10 20 30 40 50 605.000
6.000
7.000
8.000
9.000
10.000
11.000
12.000
13.000
14.000
13%10%
Days
Wt%
NaO
Cl
Half-life = 48.5 dayst=60 days, 43% original concentration
Half-life = 94.7 dayst=60 days, 60% original concentration
2nd Order Plot vs. Temperature
Decomposition Comparison (13%) Temperature Effect
0 10 20 30 40 50 604.000
5.000
6.000
7.000
8.000
9.000
10.000
11.000
12.000
13.000
14.000
68 F90 F
Days
Wt%
NaO
Cl
Rate Constant as a Function of Ionic Strength
Decomposition Comparison (90°F) HSLS vs. Typical 13%
0 10 20 30 40 50 605.000
6.000
7.000
8.000
9.000
10.000
11.000
12.000
13.000
14.000
HSLSTypical 13%
Days
Wt%
NaO
Cl
t = 60 days, 59% original concentration
t = 60 days, 43% original concen-tration
HSLS Bleach “High Strength Low Salt”
30 Wt% NaOCl◦385 GPL Available Chlorine◦≈1 Wt% NaOH◦8.5 Wt% NaCl
13 Wt% NaOCl (traditional)◦10.4 Wt% NaCl
HSLS Bleach “High Strength Low Salt”
13% Wt NaOCl (traditional)◦10.4% Wt NaCl
13% Wt HSLS - 3.7% Wt NaCl6% Wt HSLS - 1.7% Wt NaCl
It is not obvious that ionic strength might affect oxygen formation … but it does (30% less) Less oxygen ….more bleach
0 10 20 30 40 50 600.000
0.100
0.200
0.300
0.400
0.500
0.600
0.700
0.800
0.900
1.000
Oxygen Comparison (90°F)HSLS vs Typical 13%
HSLSTypical 13%
Days
Oxygen (
L g
as/L
OC
l-)
Decomposition Comparison (90°F) Transition Metal Ions
0 10 20 30 40 50 600.000
2.000
4.000
6.000
8.000
10.000
12.000
14.000
13% NaOCl0.5 mg/L Ni
Days
Wt%
NaO
Cl t = 60 days, 43% original concentration
t = 60 days, 24% original concentration
OCl- Lost … Catalyzed Reaction
Oxygen Comparison (90°F)0.5 mg/L Ni vs. Typical 13%
0 10 20 30 40 50 600.000
2.000
4.000
6.000
8.000
10.000
12.000
0.5 mg/L NiTypical 13%
Days
Oxy
gen
(L
gas
/L O
Cl-
)
t = 60 days, 11x more oxy-gen
“uncatalyzed” reaction
“catalyzed” reaction
Decomposition as a Function of pH
Chlorate Formation as a Function of pH
What Happens in UV-light ?
Unwanted By-Products
What are they ?◦Bromate BrO3-◦Chlorate ClO3-◦Perchlorate ClO4-
How do they get into the bleach?Raw materials and decomposition
Bromate Ion, BrO3-
Bromide ion in salt used to make Cl2◦Forms Br2◦Reacts with caustic to form BrO3-
Impurity in caustic
Perchlorate Ion, ClO4-
Source: Water Research Foundation, 2009, An Assessment of the Factors that Influence the Formation of Perchlorate
and Other Contaminants
ReactionOCl- + ClO3
- → ClO4- + Cl-
Strongly dependent on Temperature and Ionic Strength
Rate Lawd[ClO4
-]/dt = kClO4- [OCl-] [ClO3-]
Rate Constantlog (kClO4- ) = 0.0788(I) + log (2.084 x 1016 x T x e -1.01x10^5/RT x e -10^6/R)
Perchlorate Ion, ClO4-
0 10 20 30 40 50 600.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
40.00
45.00
50.00
Perchlorate Ion Comparison (90°F)HSLS vs Typical 13%
HSLSTypical
Days
Per
chlo
rate
Ion
(m
g/L
)
Basis of a Chemical Model
Chlorate and Oxygen Formation(3kCl + 2kox)t = 1/[OCl-]t – 1/[OCl-]0
Perchlorate Ion Formationd[ClO4
-]/dt = kClO4- [OCl-] [ClO3-]
log (kClO4- ) = 0.0788(I) + log (2.084 x 1016 x T x e -1.01x10^5/RT x e -10^6/R)
Decomposition Software Modeling
What can you model ?◦ Bleach Loss◦ Chlorate Ion Formation◦ Oxygen Formation◦ Perchlorate Ion Formation
What factors can you manipulate?◦ Concentration◦ Temperature◦ Caustic strength◦ Ionic strength◦ Metal ion concentration◦ Time parameters
Powell Software
Powell Software
0 5 10 15 20 25 300.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
0.0
5.0
10.0
15.0
20.0
25.0
30.0
Diluted HSLS Hypo vs. Traditional Hypo @ 90°F
Traditional Hypo Dilute HSLS HypoDilute HSLS Hypo GPL NaClO3 Trad. Hypo GPL NaClO3
Days
Str
ength
, w
t. %
NaO
Cl
Sodiu
m C
hlo
rate
, G
PL
Powell Software
0 5 10 15 20 25 300.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
Diluted HSLS Hypo vs. Traditional Hypo @ 90°F
Traditional Hypo Dilute HSLS HypoDilute HSLS Hypo Oxygen Trad. Hypo Oxygen
Days
Str
ength
, w
t. %
NaO
Cl
Oxygen,
LO
2/L
OC
l
Powell Software
0 5 10 15 20 25 300.0
2.0
4.0
6.0
8.0
10.0
12.0
14.0
0.0
2.0
4.0
6.0
8.0
10.0
12.0
Diluted HSLS Hypo vs. Traditional Hypo @ 90°F
Traditional Hypo Dilute HSLS HypoDilute HSLS Hypo mg/L NaClO4 Trad. Hypo mg/L NaClO4
Days
Str
ength
, w
t. %
NaO
Cl
Sodiu
m P
erc
hlo
rate
, m
g/L
Bleach Testing
Essential Analyses: (Tier 1)Wt% NaOCl g/L Available Cl2 Specific gravityWt% NaOH Wt% Na2CO3 mg/L chlorate
Optional Analyses I: (Tier 2)mg/L bromate mg/L perchlorate mg/L Fe, Cu, Ni
Optional Analysis II: (Tier 3)Filter test Dissolved SolidsSuspended Solids
ClO3- Normalized Result Calculation
INPUTS
Maximum Use Level (MUL), mg/L 80Trade % Bleach 13.475 Vol of Hypo Rec'd, mL 156.5 Vol of Peroxide, mL 31.5 Vol of Hypo Sample, mL 125 Peroxide Dilution Correction 1.25 Hypo Density, g/mL 1.2 Chlorate analysis value, mg/L 128
Normalization Factor (NF)NF = (MUL) (Peroxide Dil Correction) (1/Hypo Density) ( 1/10^3) (1/10^3) NF = 8.3475E-05
Normalized Result (NR)NR = Test Result * NF * 10^3 ug/LNR = 10.7 ug/L <200 ug/L is acceptable
Filter Test
Operations ToolParticulate matter causes problemsIn-field testing determined the parametersAt 20 inches of Hg, 1 liter of bleach should
filter through 0.8 micron filter paper in < 3 minutes
Suggested Bleach QA
Manage the Decomposition◦Concentration
TemperatureTransition Metal Ions
◦Ionic StrengthManage the Storage and DeliveryModel the Bleach and VerifyMake MeasurementsTier I analysis (minimum)
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