Understanding Bleach Degradation

Bernard Bubnis
NovaCem Laboratories, Inc.
Oxford, OH USA
www.novachemlabs.com
Sponsored by: Powell Fabrication
 NovaChem Laboratories, Inc.

Testingbleach since 1989

1990’s - AWWA Bleach Decomposition Study
Collaboration with Powell Fabrication &
Manufacturing
Decomposition Model Studies
Chemistry 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 chemistry
that 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
14.000

13.000

12.000

11.000
Wt% NaOCl

10.000
Half-life = 48.5 days
9.000 t=60 days, 43% original concentration 13%
10%
8.000

7.000
Half-life = 94.7 days
6.000 t=60 days, 60% original concentration

5.000
0 10 20 30 40 50 60

Days
2nd Order Plot vs. Temperature
 Decomposition Comparison (13%) Temperature Effect

14.000

13.000

12.000

11.000

10.000
Wt% NaOCl

9.000 68 F
90 F
8.000

7.000

6.000

5.000

4.000
0 10 20 30 40 50 60
Days
Rate Constant as a Function of Ionic Strength
 Decomposition Comparison (90°F) HSLS vs. Typical 13%

14.000
13.000
12.000
t = 60 days, 59% original concentration
11.000
Wt% NaOCl

HSLS
10.000
Typical 13%
9.000
8.000
7.000
t = 60 days, 43% original concen-
6.000
tration
5.000
0 10 20 30 40 50 60
Days
 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 NaCl
6% 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

Oxygen Comparison (90°F)

HSLS vs Typical 13%
1.000

0.900

0.800
Oxygen (L gas/L OCl-)

0.700

0.600 HSLS
Typical 13%
0.500

0.400

0.300

0.200

0.100

0.000
0 10 20 30 40 50 60

Days
 Decomposition Comparison (90°F) Transition Metal Ions

14.000

12.000

10.000

t = 60 days, 43% original concentration

Wt% NaOCl

8.000
13% NaOCl
0.5 mg/L Ni
6.000

4.000
t = 60 days, 24% original concentration

2.000

0.000
0 10 20 30 40 50 60
Days
OCl- Lost … Catalyzed Reaction
 Oxygen Comparison (90°F)
0.5 mg/L Ni vs. Typical 13%

12.000

“catalyzed” reaction
10.000
Oxygen (L gas/L OCl-)

8.000
t = 60 days, 11x more oxy- 0.5 mg/L Ni
Typical 13%
6.000 gen

4.000

2.000
“uncatalyzed” reaction
0.000
0 10 20 30 40 50 60
Days
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

Reaction
OCl- + ClO3- → ClO4- + Cl-
Strongly dependent on Temperature and Ionic Strength

Rate Law
d[ClO4-]/dt = kClO4- [OCl-] [ClO3-]

Rate Constant
log (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-

Perchlorate Ion Comparison (90°F)

HSLS vs Typical 13%
50.00

45.00

40.00
Perchlorate Ion (mg/L)

35.00

30.00 HSLS
25.00 Typical
20.00

15.00

10.00

5.00

0.00
0 10 20 30 40 50 60

Days
 Basis of a Chemical Model

Chlorate and Oxygen Formation

(3kCl + 2kox)t = 1/[OCl-]t – 1/[OCl-]0

Perchlorate Ion Formation

d[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

Diluted HSLS Hypo vs. Traditional Hypo @ 90°F

14.0 30.0

12.0 25.0
Strength, wt. % NaOCl

Sodium Chlorate, GPL

10.0
20.0
8.0
15.0
6.0
10.0
4.0

2.0 5.0

0.0 0.0
0 5 10 15 20 25 30

Days

Traditional Hypo Dilute HSLS Hypo

Dilute HSLS Hypo GPL NaClO3 Trad. Hypo GPL NaClO3
 Powell Software

Diluted HSLS Hypo vs. Traditional Hypo @ 90°F

14.0 0.8

12.0 0.7
Strength, wt. % NaOCl

0.6
10.0

Oxygen, LO2/LOCl
0.5
8.0
0.4
6.0
0.3
4.0
0.2

2.0 0.1

0.0 0.0
0 5 10 15 20 25 30

Days

Traditional Hypo Dilute HSLS Hypo

Dilute HSLS Hypo Oxygen Trad. Hypo Oxygen
 Powell Software

Diluted HSLS Hypo vs. Traditional Hypo @ 90°F

14.0 12.0

12.0 10.0

Sodium Perchlorate, mg/L

Strength, wt. % NaOCl

10.0
8.0
8.0
6.0
6.0
4.0
4.0

2.0 2.0

0.0 0.0
0 5 10 15 20 25 30

Days

Traditional Hypo Dilute HSLS Hypo

Dilute HSLS Hypo mg/L NaClO4 Trad. Hypo mg/L NaClO4
 Bleach Testing

Essential Analyses: (Tier 1)

Wt% NaOCl g/L Available Cl2 Specific gravity
Wt% 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 Solids Suspended Solids
 ClO3- Normalized Result Calculation

INPUTS

Maximum Use Level (MUL), mg/L 80

Trade % 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/L
NR = 10.7 ug/L <200 ug/L is acceptable
 Filter Test

Operations Tool
Particulate matter causes problems
In-field testing determined the parameters
At 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
Temperature
Transition Metal Ions
◦ Ionic Strength
Manage the Storage and Delivery
Model the Bleach and Verify
Make Measurements
Tier I analysis (minimum)