LONZA RESEARCH ^ftND^DEVSLQPMENT

/RESEARCH REPORT^.

TITLE HvpdBfOTSO&S Acid P h o t o s t a b i l i z a t i o n ; a T e c h n i c a l Assessment

REPORT NO/ 89-43 / DATE: December 18, 1989

AUTHOR M Ehl-Tip Sweeny CONFIDENTIAL CLASSIFICATION

LONZA CONrlDSNTIAL

RESEARCH NOTEBOOK REFERENCE{S)_ 1192: 1 5 6 " 1 9 2 _ ^ 2 0 9 i 1 ; 2 5 ^ ^_

LABORATORY WORK BY Philip Sweeny _

ABSTRACT
The New Business Development Marketing Group has identified photostable
bromine systems as a significant product development opportunity. A
technical assessment consisting of a literature review and limited _
experimentation was prepared to evaluate the feasibility of developing such a
product.
Based on this assessment it is concluded that development of a photostable
bromine system is possible. However, due to the present limited nature of
available data, it is estimated that 4.5 man months of laboratory work will
be required to determine whether photostabilization of bromine can be
economically achieved under typical pool conditions. The proposed work
consists of:
1) A systematic study of the relationship between chemical functionality,
halogen complexation and hypohalite photolysis.
2) Simulated in-pool tests to determine the overall stability of the most
promising systems.
CAS Registry Number: // Has MSDS issued?
Is material on TSCA list? // If no, has PMN been activated?

DISTRIBUTION:
Full Report Key Words
Abstract
D. Dutton DANTOBROM®
J. U. Smith Photolysis
J. Coletta
T. Farina Stability
F. Himpler Bromine
S. Shull Hypobromous acid
D. Murray
J. Pacheco

Approval_ 1.1. 4 GAAAAAL. - jidqo

 Table of Contents

I. Objective

II. Marketing Background 2

III. Technical Review 2

A. Introduction 2
B. Literature Review 3-7
1. Dark Decomposition
a-r—Pheteely&is- —-
a. HOC1
b. HOBr
c. Conclusions
3. Photostabilization
a. Cyanuric acid
b. Hydantoins
c. Glycoluril
d. Mechanisms

C. Preliminary Experimentation 7-11

1. Introduction
2. Results and Discussion
a. UV-visible data
b. Dark Decomposition and Photolysis

I. General

II. Dark Decomposition

III. Photolysis

A. Non-stabilized

B. Cyanuric acid

C. Caffeine

D. Hydantoins

E. Glycoluril

D. Conclusions 11

E. Recommendations 12

IV. Appendix 1 13-14

A. Experimental 13
Hypobromous Acid Photostabilization; a Technical Assessment

Page 2
December 18, 1989
I. Objective
The objective of this assessment is to review the technical aspects of
developing a photostable bromine system for outdoor swimming pool
applications. Ideally such a system will contain our current hydantoin
based product DANTOBROM®.

II. Marketing Background

_ . ^^g_^g^__^g^ r gjj 1 jj^^ a ,_
photostable bromine system is expected to be $7 MM/yr by the third year of
commercial use with significant annual, profitable growth thereafter (1).
A detailed review of the marketing aspects of the proposed bromine system
for outdoor pool applications is available (2).

III. Technical Review

A. Introduction
Both bromine and chlorine systems are used for biological control of
pools and spas. A major problem with such systems is that they are
susceptible to rapid photolysis when used in outdoor applications in
the absence of stabilizers. This photolysis increases the cost and
difficulty of maintaining a specific-active biocide concentration.

Bromine systems are preferred over chlorine systems since they are less
corrosive and produce less odor and eye irritation. The low odor and
eye irritation of bromines has been potulated to be a result of the
absence of nitrogen trihalide in the bromine systems (3). Chlorine
systems, however, dominate the outdoor swimming pool market since they
can be stabilized with a variety of compounds including cyanuric acid
which is the present material of consumer choice (2). The
stabilization of bromine systems including those containing Dantobrom
has proven elusive.
The goal of this investigation is to assess the feasibility of
developing a photostable bromine system to compete with the presently
used cyanuric acid/chlorine systems on a cost performance basis.

To meet the stated goal the following strategy was outlined:

1. Review literature on the dark decomposition, photolysis, and
photostabilization of hypohalites.
2. Perform limited experimentation to confirm conclusions reached
by previous workers and define halogen photostabilization
mechanisms.
3. Summarize conclusions obtained from literature review and
experimentation.
4. Recommend strategy for pursuing the development of a stabilized
bromine system based on the defined mechanisms.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 3

December 18, 1989

B. Literature Review

1. Dark Decomposition
The predominate biologically active species in bromine and chlorine
systems are hypobromous (HOBr) and hypochlorous acid (H0C1),
respectively. The decomposition of both hypobromous and
hypochlorous acid in the absence of light has been investigated at
concentrations several orders of magnitude larger than those used in
typical pool applications. To relate these data to swimming pool
applications extrapolations using the reported rate constants are
„ _ _ _ _ _ _ _ _ , _ _ _..__ _ ; _ .

Lewin and Avrahami (4) examined the effect of pH on the loss of

hypohalite from hypobromous and hypochlorous solutions as well as
combinations of the two. The initial concentration of halogen in
these studies was high, -3000 ppm as Cl_, compared to the
-1 ppm concentration typically used in pools. The rate of
hypohalite decomposition was shown to be second order. The measured
hypochlorite half-lives and those extrapolated to typical swimming
pool concentrations are shown in Table 1. The hypobromite
half-lives are shown in Table 2. Decomposition mechanisms for the
various systems were postulated. These data produce the following
conclusions:

1. The presence of hypobromite enhances the rate of hypochlorite

decomposition.
2. Hypobromite decomposition is slowed by hypochlorite due to the
reoxidation of bromide by the addition of hypochlorite.
3. The effect of increased pH is to decrease the hypohalite
decomposition rate which indicates that the dark decomposition
of the protonated hypohalite occurs more rapidly than that of
the anion. Because the pKa of hypochlorous acid is lower (7.4)
than that of hypobromous acid (8.6) this conclusion is
indicative of why bromine systems are inherently less stable
than chlorine systems to dark decomposition at pool pH's
(7.2-7.6).

Extrapolation of the reported dark decomposition rates to swimming

pool concentrations shows that:

1. The decomposition rate of hypobromite is faster than that of

hypochlorite at halogen concentrations of 5 and 1 ppm.
2. That the decomposition rates of both hypohalites are slow at
these low halogen concentrations.

Engel et al. (5) examined the loss of hypobromite from aqueous

solutions in the absence of light. These workers also used high
initial concentrations of bromine (-1400 ppm as Cl 2 ); the second
order kinetics observed by Lewin and Avrahami (4) were confirmed.
The major products in these studies were bromite and bromate; hence
the total oxidizing capacity remained constant over the short
duration of experimentation (5h).
Hypobromous Acid Photostabilization; a Technical Assessment

Page 4
December 18, 1989
The observed decomposition of hypobromite to other oxidizing species
(bromite and bromate) in this latter study emphasizes the importance
of using analytical methods which measure quantities proportional to
hypobromous acid levels not just total oxidizing capacity. This is
true since hypobromous acid is the active biocide.

2. Photolysis

a. HOC1

The rate of hypochlorous acid photolysis in sunlight has been

measured and mechanisms postulated (6-10). The referenced works
w e r e performed with the goal of defining the atmospheric
lifetime of H0C1 and deal predominantly with gas phase systems.
However, since the UV-visible absorption spectra of aqueous HOCl
solutions are similar to those of gas phase systems (6)
similarities in the photolysis rates should exist. Molina and
Molina (6) obtained a decomposition rate of 4xlO""Vs f° r H0C]-
decomposition at the earth's surface. This corresponds to a
half-life of 0.5 h for the first order reaction shown in
Equation 1. Since the photolysis reaction is first order the
measured half-lives are independent of halogen concentration and
hence these half-lives are those expected at swimming pool
halogen concentrations. The largest portion of the photolysis
was attributed to wavelengths of light between 305-355 run.

HOCl + light -> Cl« + »OH (1)

Mishalanie et al. (7) also performed a detailed investigated on

the photolysis of HOCl. These workers support the postulation
that the reaction of Equation 1 constitutes the main photolysis
pathway of HOCl. The absorption cross sections of HOCl measured
in this study were similar to those obtained by previous workers
(6,8). A value of 1 x 10"d/s was calculated for the
photolysis of HOCl at the earth's surface. This corresponds to
a half-life of 2 h.

b. HOBr

In contrast to chlorine systems, the published literature on the

photolysis of bromine systems is sparse. Subhani and Lodhi (11)
characterized the photolysis of hypobromite ion at pH of 9, 9.8,
and 12.1. The two primary photolysis processes were those of
Equations 2 and 3.

BrO- + light -> Br- + O[3p] (2)

BrO- + light -> Br« + 0- (3)

The objective of this research was to define the quantum yields

of the various reactions and no specific rate constants were
obtained.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 5
December 18, 1989

c. Conclusions
The reviewed studies produce the following conclusions
concerning hypohalite photolysis:

1) The photolysis of hypochlorous acid has been thoroughly

characterized.
2) The first order photolysis rate for hypochlorous acid is
much greater than the second order dark decomposition rate
—g-^—(jQ^j^jj^ipg^jQjyB typicHt~in swimming"pooi~app3ricat"ions
(t 1 / 2 = 1-2 h vs t 1 / a = 10 4 - 10 6 h ) .
3) Data on the photolysis of hypobromous acid is limited.

3. Photostabilization
a. Cyanuric Acid
Several materials have been examined to ascertain their ability
to decrease halogen photolysis rates. Cyanuric acid and its
salts are presently the major compounds used to photostabilize
chlorine systems (2). A review of the basic aspects of cyanuric
acid/chlorine systems has been published by Roth (12). In this
work Roth reviews the facts that :

1) Cyanuric acid stabilizes chlorine to photolysis.

2) Chlorine in the presence of cyanuric acid titrates as free
chlorine.
To explain this data Roth proposes that cyanuric acid is
functioning as an ultraviolet screen which filters out the high
energy wavelengths of sunlight responsible for photolysis.

b. Hydantoins

The structural similarities of hydantoin to cyanuric acid as

well as our interest in Dantobrom production invokes the
question of whether hydantoin derivatives can photostabilize
halogen containing systems in a manner similar to cyanuric
acid. McFarland (13) has studied the hydrolysis and photolysis
rates of l-bromo-3-chloro-5,5-dimethylhydantoin (BCDMH),
l,3-dichloro-5,5-dimethylhydantoin (DCDMH), and
l,3-dichloro-5-ethyl-5-methylhydantoin (DCEMH). The measured
half-lives of free and total halogen in the presence and absence
of light are shown in Table 3. These experiments were performed
at total halogen concentrations of -30 ppm as Cl 2 . The
following conclusions can be drawn from this data:
Hypobromous Acid Photostabilization; a Technical Assessment
Page 6
December 18, 1989
1) Light promotes the depletion of both free and total halogen
in all systems except DCDMH where the halogen decomposition
rate is rapid and relatively unaffected by light. This
observed instability of DCDMH is a result of rapid
hydantoin ring decomposition unique to this molecule and
will not be investigated further.
2) Not all halogen is free in hydantoin/chlorine/bromine
systems.
3) The halogen concentration of the bromine containing system
is_ more greatly^ffected__by_ lightjthan either of_the
chlorine systems.
c. Glycoluril

Glycoluril has been examined by Bio-Lab as a possible bromine

photostabilizer. Nechtman (14) monitored the disappearance of
bromine from a 6000 gallon pool exposed to direct sunlight in
the presence and absence of glycoluril. Summarized results of
this study are shown in Table 4. The bromine in this study was
provided by calcium hypochlorite and sodium bromide. The
results show that the half-life of total bromine increased by a
factor of -9 in the presence of glycoluril. A large
difference between the concentrations of free and total halogen
were observed in the presence of glycoluril.

A second experiment performed by Nechtman (15) involved

monitoring the bromine concentration in a 1700 gallon spa
exposed to direct sunlight. The bromine in this case was
supplied by BCDMH. Two systems were compared: One containing
glycoluril, one containing only BCDMH. The system containing
glycoluril was only slightly more stable than the control in
this latter test. Since bromine was continually added to the
systems in this experiment direct comparison with the former is
difficult. The contradictory results of the two tests
demonstrates that further work on the use of glycoluril is
necessary if an understanding of its effects on halogen
photolysis is to be obtained.

d. Mechanisms

At least two mechanisms can be postulated for the observed

behavior of cyanuric acid, hydantoins and glycoluril in halogen
containing systems. The first mechanism as proposed by Roth
for cyanuric acid ascribes UV-visible filtering capability to
the additive which reduces the intensity of the high energy
light impinging on the free halogen in solution.

A second mechanism based on the proposition that cyanuric acid,

hydantoins and glycoluril combine with halogen producing
photostable molecules is also reasonable. The hydantoin and
glycoluril containing systems show large differences between
the concentrations of free and total halogen observed
demonstrating that complexes are formed in these systems. The
mechanism by which photostabilization could occur with such
complexing agents is shown
Hypobromous Acid Photostabilization; a Technical Assessment

Page 7
December 18, 1989

in Equations 5-7, where Equation 7 represents a multiple step

degradation process. This mechanism involves the formation of a
photostable halogen complex which acts as a reservoir for free
halogen. Such systems would show lower rates of halogen loss
when compared to unstabilized systems containing equivalent
total halogen.

Stabilizer-X + H 2 0 > Stabilizer-H + HOX (5)

<

~' ~ "~ -"SEaMTIzer^ T~TlghT~ ~~=fcfor - — - (^r—

HOX + light > decomposition products (7)

It is possible that cyanuric acid functions via the mechanism of

Equations 5-7 but in this case the complex formed must be
relatively weak since only small differences are observed
between the free and total halogen measurements on cyanuric acid
containing systems.

Materials other than cyanuric acid, hydantoins and glycoluril

are known to complex with bromine. If the mechanism of
Equations 5-7 is that by which halogens are stabilized then
these materials may also slow the photolysis of halogens. For
example Jolles (16) has reviewed the ability of quaternary
ammonium halides to complex with Br2 according to Equation 8,

R4N+Br" + Br 2 -> R^N* Br3~ (8)

and the ability of tertiary amine hydrohalides to complex with

Br2 according to Equation 9.

R3H1TX- + nBr2 -> R3HN*X~nBr2 (9)

The effect of tertiary and quaternary amines on photolysis was

not reported.

C. Preliminary Experimentation

1. Introduction

Two main postulates exist for the mechanism by which additives

photostabilize halogen containing systems:

1. UV absorption capability that effectively screens the halogen

from the high energy wavelengths which produce photolysis.
2. Complexation capabilities that bind a large portion of halogen
in a photostable sink which slowly supplies free halogen into
the pool environment.

In order to confirm/negate these mechanisms for various systems and

to provide direction for future work a limited number of experiments
were performed. The details of experimentation can be found in
Appendix 1.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 8

December 18, 1989

2. Results and Discussion

a. UV-Visible Data
In order to determine the extent to which the mechanism of
halogen stabilization by UV filtration could be functioning the
UV-visible spectra of H0C1, HOBr and several possible
stabilizers were examined.

The _W^vi^s^le_d^a_ob^in^d_jg^_sh^n _in,J?ahle_.Ai. _,_The_spectral^

range presented covers the wavelength range important to solar
decomposition studies. The absorbance maximum of the HOC1
solution actually occurred at 291.4 nm with a peak absorbance of
0.05 A. This peak is in the range of that observed by previous
workers (6) for HOC1 in the presence of H 2 0. HOBr showed a
lower molar absorption coefficient and absorption at higher
wavelengths than HOCl.

The UV-visible spectra of the stabilizers examined (Table 5)

show that only glycoluril and caffeine absorb in the spectral
region of interest. Of these materials only caffeine had a
large enough absorption to effectively screen any portion of the
relevant UV spectra. The observed value of 2.8 A for the 7.75 x
10"3 molar caffeine solution indicates that this material, if
used at a molar concentration equivalent to that produced by 50
ppm cyanuric acid, would absorb 99.8% of the 295 nm light 20 cm
below the surface of a pool. Glycoluril would only absorb 13%
under the same conditions.

b. Dark Decomposition and Photolysis

I. General

The results of the dark decomposition and photolysis studies

performed are shown in Table 6. The initial free and total
halogen levels are shown in addition to the observed
half-lives to demonstrate the relative ability of the tested
materials to complex halogen.

The orders of reaction observed for both the photolysis and

dark decomposition studies were the same as those reported by
earlier workers. Plots of the natural logarithm of the
halogen concentrations vs time were linear for all studies
except the dark decomposition of HOBr. This result indicates
that the decomposition reactions were first order with
respect to halogen concentration except for the dark
decomposition of HOBr which showed some second order
deviation. The dark decomposition of HOCl could also have
been second order but this is unclear due to the slow
reaction rate and the limited time of experimentation. The
photolysis and dark decomposition studies were performed to
evaluate the stability of HOBr and HOCl and to quantitate the
photostabilizing effects of cyanuric acid, caffeine,
hydantoins and glycoluril.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 9
December 18, 1989

II. Dark Decomposition

The dark decomposition data show both HOBr and HOCl to be

relatively stable in the absence of light with HOBr having a
half-life of 189 h in spite of being 20 times more reactive
than HOCl. The observed more rapid decomposition of HOBr
than HOCl is consistent with the data of Lewin and Avrahami.
The observed 5900 h half life for HOCl is 3 times lower than
that extrapolated from the data of Lewin and Avrhami
lTable_JLl_for. 5^p^nL^sMutioji,s_.of^H0.CL.at £&, 2JLJLn_±he__.
absence of HOBr. The extrapolated hydrolysis half-life of
606 h for 5 ppm concentrations of HOBr in Table 2 exceeds the
observed rate of 189. However, these later extrapolated
values were at a higher pH (7.9 vs 7.4) which could easily
account for this difference. In general the observed values
were in the same range as those of earlier workers.

III. Photolysis

A. Non-stabilized

The photolysis of HOCl and HOBr yielded half-lives of 1.59

and 2.90 h respectively (Table 6). The HOCl value
compares favorably with the values of 0.5 h calculated by
Molina and Molina (6), 2 h calculated by Mishalanie (7),
and 1 h observed by Nechtman (Table 4). The greater
photostability of HOBr in the absence of a stabilizer may
be a result of its lower molar absorbance observed in the
UV-visible spectra.

B. Cyanuric Acid

The photolysis of HOCl and HOBr in the presence of

cyanuric acid was examined. The data of Table 6 show that
most of the halogen titrates as free in these systems as
stated by Roth (12). The half-life of the HOCl system
increased by 26 times to 41 h in the presence of cyanuric
acid. The half-life of HOBr increased by 1.9 times to
5.4 h.

The photolysis of HOCl solutions covered with a cyanuric

acid filter was also examined (Table 6) to determine if
cyanuric acid stabilizes HOCl through UV absorption. A
half-life of 1.34 h was observed which is equivalent to
that obtained for the unstabilized system. This result
indicates that cyanuric acid does not stabilize HOCl
through UV filtration as proposed by Roth (12). An
alternate postulate to the mechanism by which cyanuric
acid stabilizers HOCl is the one of Equations 5-7 with the
stipulation that the halogen complex must be weak and
titrate as free.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 10
December 18, 1989

C. Caffeine

The use of a caffeine filter to stabilize HOBr was also

tested (see Table 6). The observed half-life was 2.72
hours which is within experimental error of the results of
the photolysis control. Caffeine was the material having
the highest molar absorbance of those examined (see
Table 5). The failure of caffeine to photostabilize HOBr
indicates that none of the other materials examined can
stabilize HOBr through a UV filtering mechanism.

D. Hydantoins

The effect of DMH on the photolysis of HOCl and HOBr was

examined (see Table 6). DMH complexed with HOCl yielding
high total but little free halogen. The half-life of
halogen observed was 115 h which is 2.8 times that
observed for the cyanuric acid/HOCl system and 72 times
that of the unstabilized system. The enhanced stability
of HOCl observed in the presence of DMH seems to
contradict the data of Table 3 which shows DCDMH to have
low stability. These differences are probably
attributable to the formation of monochloro DMH as opposed
to unstable DCDMH in the presently reported system. The
effect of DMH on HOBr was to slightly reduce the ratio of
free to total halogen and to produce a half-life of
4.8 h. This value is 1.7 times greater than the control
and similar to that produced by cyanuric acid.

DMH photostabilizes chlorine to a greater extent than

cyanuric acid. However, difficulty would occur with the
use of this material in a pool application due to the low
concentrations of free halogen which would be incurred.
DMH produces some photostabilization of HOBr, apparently
by a complexation mechanism, but, the degree of
stabilization is small and no greater than that observed
for cyanuric acid.

E. Glycoluril

Glycoluril was added to both HOCl and HOBr to test its

effect on photolysis (see Table 6). This material
complexed with HOCl producing high total but little free
chlorine. The half-life observed was 24.8 h which is 16
times greater than the control but 1.7 times smaller than
that observed for cyanuric acid. Glycoluril slightly
reduced the ratio of free to total halogen in the HOBr
system. The half-life of bromine decreased to 0.87 h
under these conditions, a destabilization of 3.3 times.
Comparison of this data with that of Nechtman in Table 4
shows a major inconsistency between the two data sets.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 11
December 18, 1989
Glycoluril does not photostabilize chlorine systems as
efficiently as cyanuric acid. Contradictory evidence
exists concerning its function in bromine systems.
Perhaps the order of addition of glycoluril/HOCl/NaBr is
critical. An unknown order of addition was used by
Nechtman. The order of addition in the present studies
was 1) H0C1, 2) NaBr, and 3) glycoluril. If glycoluril
was first mixed with H0C1 perhaps the complex formed would
be relatively stable and hence only yield HOBr slowly upon
the addition of NaBr. The glycoluril chlorine system did
^projdjacje_a_strong cjilorine_.complex,4. _ ;

D. Conclusions

The goal of producing a bromine system with a photostability similar to

that of cyanuric acid/chlorine system appears possible. This
conclusion is based on the observation that the dark decomposition rate
of HOBr is slower than the photolysis of cyanuric acid/chlorine
systems.

No bromine system examined to date has produced the same photostability

as that observed for cyanuric acid/chlorine systems. Chlorine systems
are photostabilized by a variety of materials, the order of stability
being DMH > cyanuric acid > glycoluril. Bromine systems are
photostabilized by DMH and cyanuric acid. The effect of these two
compounds is similar with the degree of stability produced being -10
times less than that observed for cyanuric acid/chlorine systems. The
effect of glycoluril on bromine systems is unclear and needs further
characterization.

Two different mechanisms have been postulated for the

photostabilization of halogen systems:

1. Ultraviolet screening, and

2. Photostable complex formation.
Present evidence indicates that the latter mechanism is the one in
operation for all stabilizers reviewed.

Several chemical functionalities in addition to those initially

examined are known to complex halogen, e.g., tertiary and quaternary
amines. In order to thoroughly characterize the relationship between
chemical structure, halogen complexation, and photostabilization, these
materials need to be evaluated.

The analytical methods used to monitor the photostability of HOC1 and

HOBr need to be clearly defined and the effects of possible interfering
species such as bromite and bromate described.

In order to correlate lab performance to pool performance simulated

in-pool tests are necessary since factors other than photostability,
i.e., volatility and ammonia complexation are known to influence
halogen stability.
Hypobromous Acid Photostabilization; a Technical Assessment
Page 12
December 18, 1989

E. Recommendations

The following actions are required to determine if a photostable

bromine system can be developed which can compete with cyanuric
acid/chlorine systems on a cost performance basis in outdoor pool
applications.

1. Experimentation to define chemical functionalities which can produce

p h o t a s t a b l e 4 « a m i n © ^ * y s t © ^ —

2. Secondary factors which may effect bromine stability are

concentration of bromide and method of bromine generation. Limited
experimentation is necessary to define the importance of these
factors (0.5 man months).

3. Definition and characterization of analytical procedures for

monitoring the proposed halogen decomposition and photolysis
reactions (0.25 man months).

4. The UV-visible spectra of chlorine and bromine systems have

indicated that the spectral range responsible for the majority of
photolysis is 300-350 ran. Examination of the UV-visible spectrum of
all materials shown to stabilize halogen systems (0.25 man months).

5. Simulated in-pool tests of the bromine systems showing the highest

stability should be compared with cyanuric acid/chlorine systems to
determine total system stability (1 man month).

6. Preparation of final report (0.5 man months).

The total resources necessary to complete the above experimentation is

4.5 man months. The economic benefits which would be achieved from the
development of a photostable bromine system seems to warrant this
commitment.

The degree of technical risk for this project is medium-high to high.

Hypobromous Acid Photostabilization; a Technical Assessment
Page 13
December 18, 1989

IV. Appendix 1

A. Experimental

Halogen titrations

Several titrometric methods were examined to establish a procedure for

quantitating free and total halogen. The procedures selected for
measuring free and total halogen were the Standard Methods for the
examination of Water and Wastewater Method 408 D procedures al and a3
js^spae&iveiyr— She—tits»fci©»s-w©s«-p«*£©£ffl©4-fey4-—-

1. Titrating DPD indicator with Ferrous Ammonium Sulfate (FAS) to

obtain the concentration of free halogen
2. Adding 10ml 15% KI, waiting two minutes
3. Titrating the total halogen.

In some cases the Glyco standard analytical method (SAM) R-120

(thiosulfate/KI) was used to determine the total halogen concentration,
but the aforementioned DPD methods were used unless specifically
mentioned otherwise.

UV-Visible Spectra

The UV-visible spectra were obtained on a Perkin Elmer Lambda 4B using

cells of 1 cm path length, distilled water as the reference, a scan
rate of 120 nm/min, and a scan range of 250-400 run. The concentrations
of the stabilizer solutions examined were 7.75 x 10"3 M (Notebook:
1192-106, 100). The concentration is equivalent to that produced by
1000 ppm of cyanuric acid. This concentration was selected to mimic
the UV filtration effect expected at 20 cm below the surface of pool
containing 50 ppm cyanuric acid. The HOCl solution was prepared by
dilution of "5%" NaOCl solution with distilled water to achieve 8 ppm
as Cl 2 as measured by Kl/thiosulfate (Notebook: (192-174). The HOBr
solution was prepared from the diluted NaOCl solution to which one
equivalent of NaBr was added. The concentration of halogen in the
hypobromous solution was 7 ppm total halogen as Cl 2 by thiosulfate/KI
(Notebook: 1192-133).

Solution Preparation

The standard method for preparing HOCl and HOBr solutions for the dark
decomposition studies and the photolysis studies was as follows. HOCl
solutions were prepared by diluting 0.15 mL "5%" NaOCL with 1 L buffer
solution. The buffer solution was prepared from the dissolution of
21.72 g Na2HPO4 and 13.32g KH2PO4 in 3 L distilled water and
adjusting the pH to 7.4 using 0.5 N KOH. HOBr solutions were prepared
from the addition of 0.01023 g NaBr to the aforementioned HOCl
solutions. This corresponds to 1.1 equivalents of the total halogen
measured in the HOCl solutions. In cases where- stabilizers were being
evaluated, stabilizer concentrations of 3.35 x 10" 4 M were used.
This concentration corresponds to that produced by 50 ppm cyanuric
acid.
 Hypobromous Acid Photostabilization; a Technical Assessment
Page 14
December 18, 1989

Appendix 1 cont.

Dark Decomposition Studies

These experiments were performed by preparing solutions of HOCl and

HOBr in 1 L volumetric flasks and storing them in the dark over the
diira±ian_.a£ ±he~experij»ent^_E«si«4i©aA^ ft3r~
titration.
Photolysis Studies

These studies were performed using a UVA-340 ultraviolet light source

designed to imitate the high energy spectrum of the sun impinging on
the earths surface (300-360 nm). Solutions of HOCl and HOBr were
prepared and 100 ml added to 125 ml jars approximately 5 cm in diameter
and 6 cm high. The jars were covered with filter cells comprised of
4.5 cm diameter, 1 cm high steel rings attached to two 2 mm thick
quartz plates. These filter cells were normally filled with distilled
water but in some cases were filled with materials being examined as UV
absorbers. The covered jars were placed in a constant temperature bath
-9 cm below the UV source.

PGS/jb
 TABLE 1

Hypochlorite Dark Decomposition*

Cl initial Br initial
pH as ppm Cl 2 as ppm Cl 2 t 1/2 of C l 2 (h)
7 .0 3110 0 22
7 .0 5 0 1.37 x 10 4 b

7 .0 1 0 6.85 x 10 4 b

7 .0 2600 637 0.17

b
7 .0 5 1.2 87
b
7 .0 1 0.25 433

7 .9 2700 0 394
7 .9 5 0 2.1 x 10 s b

7 .9 1 0 1.1 x 10 s b

7 .85 2050 573 0.50

b
7 .85 5 1.4 204
b
7 .85 1 0.28 1020

a
Lewin and Avrahami (4)
b
Extrapolated values
 TABLE 2

Hypobromite Dark Decomposition*

Cl initial Br initial
_JDH_ as ppm Cl 2 as ppra Br 2 t 1/2 of Br 2 (h)

~T7T IT • rw~ trr

7.9 0 5 606 b

7.9 0 1 3030 b

7.85 2050 573 190

7.85 18 5 2.2 x 1 0 4 b

7.85 3.6 1 1.1 X 1 0 5 b

* Lewin and Avrahami (4)

13
Extrapolated values
 TABLE 3

Halohydantoins
Hydrolysis/Photolysis15

Conditions: pH 7.0, 25°C

light initial free initial total halogen t 1/2 of free t 1/2 of total
Compound present as ppm Cl as ppm Cl?. halogen (h) halogen (h)
DCDMH No 9.0 30.5 3 4
Yes 9.0 30.5 1 5

DCMEH No 15.8 34.0 10 >30

Yes 15.0 33.0 3 20

BCDMH No 13.0 25.8 >>30 >30

Yes 13.0 25.8 30 6

McFarland (13)
 TABLE 4

Bromine PhotolysisBL , 15

Conditions: pH=7.0 assumed, T=65-80°F

Glycoluril Initial free bromine Initial total bromine t 1/2 free bromine t 1/2 total
Cone., ppm as ppm Cl 2 as ppm Cl 2 bromine (h) bromine (h)
0 9.0 9 .0 i 1
25 2.0 16 . 0 8.5
50 1.0 17 . 0 variable 9

* Nechtman (14)
to
Br supplied by Ca(OCl)2 + NaBr
 TABLE 5

UV-Visible Spectra, 295-400nm

Compound lamda max (nm) Abs (A)

H2O <TT. 01
Succinimide <0.01

Acetamide <0.01

DMH <0.01

Sustain^ <0.01

Cyanuric acid <0.01

Glycoluril 320 0.06

Caffeine <295 2.8 (at 295nm)

HOC1 <295 0.05 (at 295nm)

HOBr 330 0.01

Commercial "Algae Shield"

 TABLE 6

H0C1 and HOBr Dark Hydrolysis and Photolysis Studies'

Initial free Initial total
Light/ Coraplexing halogen as halogen as free total
Halogen Filter Agent Data set ppm Cl 2 ppm Cl 2 t 1/2 h t 1/2 h
HOC1 Darkb 1192-169 5.2 5.9 ~10 4 3900
HOBr Dark to 1192-170 4.4 5.0 185 + 12 189 + 15
HOC1 .UV/H2O 1192-182 5.8 6.5 1 .48 + 0.10 1.59 + 0.07

HOBr UV/H2O 1192-195 4.6 5.3 2 .63 + 0.05 2.90 + 0.12

HOC1 UV/H2O Cyanuric 1209-9 6.3 7.1 53 + 11 41 + 4

Acid
HOBr UV/H2O Cyanuric 1209-20 4.3 4.9 4.9 + 0.6 5.4 + 0.4
Acid
HOC1 UV/ 1209-31 5.8 6.6 1.8 + 0.04 1.34 + 0.03
Cyanuric Acid
HOBr UV/ 1209-5 4.4 4.8 2 .71 + 0.16 2.72 + 0.13
Caffeine
HOC1 UV/H2O DMH 1209-21 0.4 6.7 6 + 3 115 + 32
HOBr UV/H2O DMH 1209-22 3.8 5.5 5.6 + 0.5 4.8 + 0.3

HOC1 UV/H2O Glycoluril 1209-23 0.1 6.8 9 + 3 24.8 + 1.4

HOBr UV/H2O Glycoluril 1209-25 4.4 6.1 0 .30 + 0.06 0.87 + 0.15

* T = 26 + 1°C, pH = 7.40 + 0.05

b
T = 20°C
 REFERENCES

1. Coletta, J; Pacheco, J.F. Project Definition Sheet May 23,

1989.
2. Coletta, J.; Pacheco J.F. Memo on "DANTOBROM® -
Hypobromous Acid stabilization R & D Project Request" May
23, 1989.
3. Jolles, Z.E. "Bromine and its Compounds" New York: Academic
Press, 1966, p. 554-562.
4. Lewin, M.; Avrahami, M. JACS 1955, 77, 4491.
-5~. —E^eXT^F-T^Sp^^tXa^-KTi p- er t^t1:er^^
2010.
6. Molina, L.T.; Molina, M.J. J. Phys. Chem. 1978, 82 (22),
2410.
7. Mishalanie, E.A.; Rutkowski, C.J.; Hutte, R.S.; Birks, J.W.
J. Phys. Chem. 1986, 90, 5578.
8. Knauth, H.D.; Alberti, H.; Clausen, H. J. Phys. Chem. 1979,
83 (12), 1604.
9. Su, F.; Calvert, J.G.; Lindley, C.R.; Uselman, W.M.; Shaw,
J.H. J. Phys. Chem. 1979, 86, 90, 5578.
10 Molina, M.J.; Ishiwata, T.; Molina, L.T. J. Phys. Chem.
1980, 84, 821.
11. Subhani, M.S.; Lodhi, S.F. Revue Roumaine de Chemie 1980, 25
(11-12), 1567.
12. Roth, E.S. Swimming Pool Weekly/Swimming Pool Age Feb. 24,
1969.
13. McFarland, A.G. "Hydrolysis/Photolysis of Halogenated
Hydantoins" Glyco Research Report 85-62 Dec. 9, 1985.
14. Nechtman, J. "Bromine-Glycoluril Stabilizer Screen" Biolab
report 4/25-26/89.
15. Ibid 8/1-10/89.
16. Jolles, Z.E. "Bromine and Its Compounds" New York: Academic
Press, 1966, p. 326, 368, 561.
 LONZA RESEARCH AND DEVELOPMENT

RESEARCH REPORT

TITLE Hypobroroous Acid Photostabilization; a Technical Assessment

REPORT NO. 89-43 DATE: December 18, 1989
AUTHOR Philip Sweeny CONFIDENTIAL CLASSIFICATION
LOMZA CONFIDENT XAXJ

RESEARCH NOTEBOOK REFERENCE(S) 1192:156-192 1209:1-25, 31

,-^^gg^^^^

ABSTRACT

The New Business Development Marketing Group has identified photostable

bromine systems as a significant product development opportunity. A
technical assessment consisting of a literature review and limited
experimentation was prepared to evaluate the feasibility of developing such a
product.

Based on this assessment it is concluded that development of a photostable

bromine system is possible. However, due to the present limited nature of
available data, it is estimated that 4.5 man months of laboratory work will
be required to determine whether photostabilization of bromine can be
economically achieved under typical pool conditions. The proposed work
consists of:

1) A systematic study of the relationship between chemical functionality,

halogen complexation and hypohalite photolysis.
2) Simulated in-pool tests to determine the overall stability of the most
promising systems.

CAS Registry Number: // Has MSDS issued?

Is material on TSCA list? // If no, has PMN been activated?
DISTRIBUTION:
Abstract Full Report Key Words
J. U. Smith D. Dutton DANTOBROM®
J. Coletta Photolysis
T. Farina Stability
F. Himpler Bromine
S. Shull Hypobromous acid
D. Murray
J. Pacheco
Approval 1. i. 1 QSUAAZU 11 / 2^/90
 Table of Contents

Page #
I. Objective 2

II- Marketing Background 2

III. Technical Review 2

A. Introduction 2

B. Literature Review 3_7

1. Dark Decomposition
2 ^ Photolysis
" a". HOC!
b. HOBr
c. Conclusions
3. Photostabilization
a. Cyanuric acid
b. Hydantoins
c. Glycoluril
d. Mechanisms

C. Preliminary Experimentation 7_H

1. Introduction
2. Results and Discussion
a. UV-visible data
b. Dark Decomposition and Photolysis

I. General

II. Dark Decomposition

III. Photolysis

A. Non-stabilized

B. Cyanuric acid

C. Caffeine

D. Hydantoins

E. Glycoluril

D. Conclusions ,«

E. Recommendations ^2

IV. Appendix 1 13-14

A. Experimental 13
'Hypobromous Acid Photostabilization; a Technical Assessment

Page 2
December 18, 1989

I. Objective

The objective of this assessment is to review the technical aspects of

developing a photostable bromine system for outdoor swimming pool
applications. Ideally such a system will contain our current hydantoin
based product DANTOBROM®.

II. Marketing Background

The new revenue which wc^d_^_g^nej>ated__bjy_the develgpment of a

pHotos"tS)le"bromine "systeirTis~exp"eoted' to~be~$7~im7yr by thVthird year of
commercial use with significant annual, profitable growth thereafter (1).
A detailed review of the marketing aspects of the proposed bromine system
for outdoor pool applications is available (2).

III. Technical Review

A. Introduction

Both bromine and chlorine systems are used for biological control of
pools and spas. A major problem with such systems is that they are
susceptible to rapid photolysis when used in outdoor applications in
the absence of stabilizers. This photolysis increases the cost and
difficulty of maintaining a specific-active biocide concentration.

Bromine systems are preferred over chlorine systems since they are less
corrosive and produce less odor and eye irritation. The low odor and
eye irritation of bromines has been potulated to be a result of the
absence of nitrogen trihalide in the bromine systems (3). Chlorine
systems, however, dominate the outdoor swimming pool market since they
can be stabilized with a variety of compounds including cyanuric acid
which is the present material of consumer choice (2). The
stabilization of bromine systems including those containing Dantobrom
has proven elusive.

The goal of this investigation is to assess the feasibility of

developing a photostable bromine system to compete with the presently
used cyanuric acid/chlorine systems on a cost performance basis.

To meet the stated goal the following strategy was outlined:

1. Review literature on the dark decomposition, photolysis, and
photostabilization of hypohalites.
2. Perform limited experimentation to confirm conclusions reached
by previous workers and define halogen photostabilization
mechanisms.
3. Summarize conclusions obtained from literature review and
experimentation.
4. Recommend strategy for pursuing the development of a stabilized
bromine system based on the defined mechanisms.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 3

December 18, 1989

B. Literature Review

1. Dark Decomposition
The predominate biologically active species in bromine and chlorine
systems are hypobromous (HOBr) and hypochlorous acid (HOCl),
respectively. The decomposition of both hypobromous and
hypochlorous acid in the absence of light has been investigated at
concentrations several orders of magnitude larger than those used in
typical pool applications. To relate these data to swimming pool
applications extrapolations using the reported rate constants are
necessary_.

Lewin and Avrahami (4) examined the effect of pH on the loss of

hypohalite from hypobromous and hypochlorous solutions as well as
combinations of the two. The initial concentration of halogen in
these studies was high, -3000 ppm as Cl 2 , compared to the
-1 ppm concentration typically used in pools. The rate of
hypohalite decomposition was shown to be second order. The measured
hypochlorite half-lives and those extrapolated to typical swimming
pool concentrations are shown in Table 1. The hypobromite
half-lives are shown in Table 2. Decomposition mechanisms for the
various systems were postulated. These data produce the following
conclusions:

1. The presence of hypobromite enhances the rate of hypochlorite

decomposition.
2. Hypobromite decomposition is slowed by hypochlorite due to the
reoxidation of bromide by the addition of hypochlorite.
3. The effect of increased pH is to decrease the hypohalite
decomposition rate which indicates that the dark decomposition
of the protonated hypohalite occurs more rapidly than that of
the anion. Because the pKa of hypochlorous acid is lower (7.4)
than that of hypobromous acid (8.6) this conclusion is
indicative of why bromine systems are inherently less stable
than chlorine systems to dark decomposition at pool pH's
(7.2-7.6).

Extrapolation of the reported dark decomposition rates to swimming

pool concentrations shows that:

1. The decomposition rate of hypobromite is faster than that of

hypochlorite at halogen concentrations of 5 and 1 ppm.
2. That the decomposition rates of both hypohalites are slow at
these low halogen concentrations.

Engel et al. (5) examined the loss of hypobromite from aqueous

solutions in the absence of light. These workers also used high
initial concentrations of bromine (-1400 ppm as Cl 2 ); the second '
order kinetics observed by Lewin and Avrahami (4) were confirmed.
The major products in these studies were bromite and bromate; hence
the total oxidizing capacity remained constant over the short
duration of experimentation (5h).
Hypobromous Acid Photostabilization; a Technical Assessment

Page 4
December 18, 1989

The observed decomposition of hypobromite to other oxidizing species

(bromite and bromate) in this latter study emphasizes the importance
of using analytical methods which measure quantities proportional to
hypobromous acid levels not just total oxidizing capacity. This is
true since hypobromous acid is the active biocide.

2. Photolysis

a. HOC1

The rate of hypochlorous acid photolysis in sunlight has been

measured and mechanisms postulated (6-10). The referenced works
were performed with the goal of defining the atmospheric
lifetime of HOCl and deal predominantly with gas phase systems.
However, since the UV-visible absorption spectra of aqueous HOCl
solutions are similar to those of gas phase systems (6)
similarities in the photolysis rates should exist. Molina and
Molina (6) obtained a decomposition rate of 4xl0~4/s for HOCl
decomposition at the earth's surface. This corresponds to a
half-life of 0.5 h for the first order reaction shown in
Equation 1. Since the photolysis reaction is first order the
measured half-lives are independent of halogen concentration and
hence these half-lives are those expected at swimming pool
halogen concentrations. The largest portion of the photolysis
was attributed to wavelengths of light between 305-355 nm.

HOCl + light -> Cl« + »0H (1)

Mishalanie et al. (7) also performed a detailed investigated on

the photolysis of HOCl. These workers support the postulation
that the reaction of Equation 1 constitutes the main photolysis
pathway of HOCl. The absorption cross sections of HOCl measured
in this study were similar to those obtained by previous workers
(6,8). A value of 1 x 10-"/s was calculated for the
photolysis of HOCl at the earth's surface. This corresponds to
a half-life of 2 h.

b. HOBr

In contrast to chlorine systems, the published literature on the

photolysis of bromine systems is sparse. Subhani and Lodhi (11)
characterized the photolysis of hypobromite ion at pH of 9, 9.8,
and 12.1. The two primary photolysis processes were those of
Equations 2 and 3.

BrO- + light -> Br- + 0[3p] (2)

BrO- + light -> Br* + 0 - (3)

The objective of this research was to define the quantum yields

of the various reactions and no specific rate constants were
obtained.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 5
December 18, 1989

c. Conclusions
The reviewed studies produce the following conclusions
concerning hypohalite photolysis:

1) The photolysis of hypochlorous acid has been thoroughly

characterized.
2) The first order photolysis rate for hypochlorous acid is
much greater than the second order dark decomposition rate
ajt_coj5cj3ntrjati^ in_sjjijratdnc[_pjool_§££ljjcatipj^___
(t i / 2 = 1-2 h vs t a / a = 10* - 10 6 h ) .
3) Data on the photolysis of hypobromous acid is limited.

3. Photostabilization
a. Cyanuric Acid

Several materials have been examined to ascertain their ability

to decrease halogen photolysis rates. Cyanuric acid and its
salts are presently the major compounds used to photostabilize
chlorine systems (2). A review of the basic aspects of cyanuric
acid/chlorine systems has been published by Roth (12). In this
work Roth reviews the facts that :

1) Cyanuric acid stabilizes chlorine to photolysis.

2) Chlorine in the presence of cyanuric acid titrates as free
chlorine.

To explain this data Roth proposes that cyanuric acid is

functioning as an ultraviolet screen which filters out the high
energy wavelengths of sunlight responsible for photolysis.
b. Hydantoins

The structural similarities of hydantoin to cyanuric acid as

well as our interest in Dantobrom production invokes the
question of whether hydantoin derivatives can photostabilize
halogen containing systems in a manner similar to cyanuric
acid. McFarland (13) has studied the hydrolysis and photolysis
rates of l-bromo-3-chloro-5,5-dimethylhydantoin (BCDMH),
l,3-dichloro-5,5-dimethylhydantoin (DCDMH), and
l,3-dichloro-5-ethyl-5-methylhydantoin (DCEMH). The measured
half-lives of free and total halogen in the presence and absence
of light are shown in Table 3. These experiments were performed
at total halogen concentrations of -30 ppm as Cl 2 . The
following conclusions can be drawn from this data:
Hypobromous Acid Photostabilization; a Technical Assessment
Page 6
December 18, 1989

1) Light promotes the depletion of both free and total halogen

in all systems except DCDMH where the halogen decomposition
rate is rapid and relatively unaffected by light This
observed instability of DCDMH is a result of rapid
hydantoin ring decomposition unique to this molecule and
will not be investigated further.
2) Not all halogen is free in hydantoin/chlorine/bromine
systems.
3) The halogen concentration of the bromine containing system
is more greatly affected by light than either of the
duonne -systems-;- — • -
c. Glycoluril

SniJ ii ! e ? a m i n e d b*Bio"Lab as a possible bromine

photostabilizer. Nechtman (14) monitored the disappearance of
bromine from a 6000 gallon pool exposed to direct sunlight in
the presence and absence of glycoluril. Summarized results of
n ^ f r f I ^ e shown in Table 4. The bromine in this study was
provided by calcium hypochlorite and sodium bromide. The
tlrtlt* ? « t h a L t h 6 half life of
" ^ a l bromine increased by a
factor of ~9 m the presence of glycoluril. A large
difference between the concentrations of free and total haloaen
were observed in the presence of glycoluril. Imogen

A second experiment performed by Nechtman (15) involved

monitoring the bromine concentration in a 1700 gallon spa
exposed to direct sunlight. The bromine in this case was
suppliedby BCDMH. Two systems were compared: One containing
glycoluril, one containing only BCDMH. The system containing
glycoluril was only slightly more stable than the control in
ovi?«;a"er^® S i n e bromine was
° continually added to the
systems in this experiment direct comparison with the former is
difficult. The contradictory results of the two tests
o f its effects n haio n
demonstrates that further work on the use of glycoluril is

ss^i^rssss ° -
d. Mechanisms

At least two mechanisms can be postulated for the observed

light impinging on the free halogen in solution.

A second mechanism based on the proposition that cyanuric acid

f j 1 . ^ and glycoluril combine with halogen producing '
photostable molecules is also reasonable. The hydantoin and
C aining YStBmS S h W larg6
llr£Zil °? *
the concentrations l ° halogen
of free and total differences
observedbSwSn
demonstrating that complexes are formed in these systems. The
c ^ i ^ ^ f i f i°riiization couid —*with ^
Hypobromous Acid Photostabilization; a Technical Assessment

Page 7
December 18, 1989

in Equations 5-7, where Equation 7 represents a multiple step

degradation process. This mechanism involves the formation of a
photostable halogen complex which acts as a reservoir for free
halogen. Such systems would show lower rates of halogen loss
when compared to unstabilized systems containing equivalent
total halogen.

Stabilizer-X + H 2 0 > Stabilizer-H + HOX (5)

>f|||M[
Stabi]Jjwr=X-J=--liglit -$•*> • (€r)

HOX + light > decomposition products (7)

It is possible that cyanuric acid functions via the mechanism of

Equations 5-7 but in this case the complex formed must b e
relatively weak since only small differences are observed
between the free and total halogen measurements o n cyanuric acid
containing systems.

Materials other than cyanuric acid, hydantoins and glycoluril

are known t o complex with bromine. If the mechanism o f
Equations 5-7 is that by which halogens are stabilized then
these materials may also slow the photolysis of halogens. F o r
example Jolles (16) has reviewed the ability of quaternary
ammonium halides t o complex with B r 2 according to Equation 8,

R d N * B r ~ + B r 2 -> R^N"1" B r 3 ~ (8)

and the ability o f tertiary amine hydrohalides to complex with

B r 2 according t o Equation 9.

R 3 H1TX- + n B r 2 -> R 3 fflTX-nBr a (9)

The effect o f tertiary and quaternary amines o n photolysis was

not reported.

C. Preliminary Experimentation

1. Introduction

Two main postulates exist for the mechanism b y which additives

photostabilize halogen containing systems:

1. UV absorption capability that effectively screens the halogen

from the high energy wavelengths which produce photolysis.
2. Complexation capabilities that bind a large portion o f halogen
in a photostable sink which slowly supplies free halogen into
the pool environment.

In order to confirm/negate these mechanisms for various systems and

to provide direction for future work a limited number o f experiments
were performed. The details of experimentation can b e found in
Appendix 1.
Hypobromous Acid Photostabilization; a Technical Assessment
Page 8
December 18, 1989

2. Results and Discussion

a. UV-Visible Data

Xi™ ^o determine the extent to which the mechanism of

n? v f KI ! a t l ° n bY W filtrati
° " ^uld be functioning the
UV-visible spectra of HOCl, HOBr and several possible
stabilizers were examined.

The UV-visible data obtained are shown in Table 5. The spectral

" ^^^e^d^cova^hewav^en^range-^portS^^^-
decomposition studies. The absorbance m a x i m of the HOCl
0 A 0 " This
05 A.
0.05
Y
v O Cis
? h i ^peak CUrre
! a t range
m the
291 4 m W i t h a
* e a k «*»°rbanee
" of that observed of
by previous
6>
Wlower
^ K" H °. C 1 ^thS PreS6nC6 ° f H =°-
molar absorption coefficient and absorption at hioher
H0B
r showedl
wavelengths than HOCl. nigner

The UV-visible spectra of the stabilizers examined (Table 5)

show that only glycoluril and caffeine absorb in the spectral
region of interest. Of these materials only caffeine had a
large enough absorption to effectively screen any portion of the
relevant UV spectra. The observed value of 2.8 I ?°r the 7 75 *
m C f f 6 i n e S 1 U U o n indicatesthat
III ? ^ f ° this mSrial, i?
used at a molar concentration equivalent to that produced bv 50

STSrSaSr-SM aas « ?
b. Dark Decomposition and Photolysis

I. General

halogen levels are shown in addition to the observed

half-lives to demonstrate the relative ability of the tested
materials to complex halogen. tested

The orders of reaction observed for both the photolysis and

dark decomposition studies were the same as those reported by
earlier workers. Plots of the natural logarithm of S T
«i«? n i.s o n r n i r ; t i o n B vs time were iinear f r an s t
° ^ies
that th J decomposition of HOBr. This result indicates
that the decomposition reactions were first order with
respect to halogen concentration except for the dark
decomposition of HOBr which.showed some second order
deviation The dark decomposition of HOCl could also have
been second order but this is unclear due to the slow
Total? %*f thB, limited time Of cementation. The
photolysis and dark decomposition studies were performed to
evaluate the stability of HOBr and HOCl and to ^ a S a t e the
Hypobromous Acid Photostabilization; a Technical Assessment

Page 9
December 18, 1989

II. Dark Decomposition

The dark decomposition data show both HOBr and H0C1 to be

relatively stable in the absence of light with HOBr having a
half-life of 189 h in spite of being 20 times more reactive
than HOCl. The observed more rapid decomposition of HOBr
than HOCl is consistent with the data of Lewin and Avrahami.
The observed 3900 h half life for HOCl is 3 times lower than
that extrapolated from the data of Lewin and Avrhami
(Table 1) for 5 ppm solutions of HOCl at pH 7.0 in the
absence-of-JHOBr,—Ihe-extrapolat«44ij4£©4^f*4s-feaif-4r4#e- ©f-
606 h for 5 ppm concentrations of HOBr in Table 2 exceeds the
observed rate of 189. However, these later extrapolated
values were at a higher pH (7.9 vs 7.4) which could easily
account for this difference. In general the observed values
were in the same range as those of earlier workers.

III. Photolysis

A. Non-stabilized

The photolysis of HOCl and HOBr yielded half-lives of 1.59

and 2.90 h respectively (Table 6). The HOCl value
compares favorably with the values of 0.5 h calculated by
Molina and Molina (6), 2 h calculated by Mishalanie (7),
and 1 h observed by Nechtman (Table 4). The greater
photostability of HOBr in the absence of a stabilizer may
be a result of its lower molar absorbance observed in the
UV-visible spectra.

B. Cyanuric Acid

The photolysis of HOCl and HOBr in the presence of

cyanuric acid was examined. The data of Table 6 show that
most of the halogen titrates as free in these systems as
stated by Roth (12). The half-life of the HOCl system
increased by 26 times to 41 h in the presence of cyanuric
acid. The half-life of HOBr increased by 1.9 times to
5.4 h.

The photolysis of HOCl solutions covered with a cyanuric

acid filter was also examined (Table 6) to determine if
cyanuric acid stabilizes HOCl through UV absorption. A
half-life of 1.34 h was observed which is equivalent to
that obtained for the unstabilized system. This result
indicates that cyanuric acid does not stabilize HOCl
through UV filtration as proposed by Roth.(12). An
alternate postulate to the mechanism by which cyanuric
acid stabilizers HOCl is the one of Equations 5-7 with the
stipulation that the halogen complex must be weak and
titrate as free.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 10
December 18, 1989

C. Caffeine

The use of a caffeine filter to stabilize HOBr was also

tested (see Table 6). The observed half-life was 2.72
hours which is within experimental error of the results of
the photolysis control. Caffeine was the material having
the highest molar absorbance of those examined (see
Table 5). The failure of caffeine to photostabilize HOBr
indicates that none of the other materials examined can
stabilize HOBr through a UV filtering mechanism.

~ &7-Hyaanto±ms

The effect of DMH on the photolysis of H0C1 and HOBr was

examined (see Table 6). DMH complexed with HOCl yielding
high total but little free halogen. The half-life of
halogen observed was 115 h which is 2.8 times that
observed for the cyanuric acid/HOCl system and 72 times
that of the unstabilized system. The enhanced stability
of HOCl observed in the presence of DMH seems to
contradict the data of Table 3 which shows DCDMH to have
low stability. These differences are probably
attributable to the formation of monochloro DMH as opposed
to unstable DCDMH in the presently reported system. The
effect of DMH on HOBr was to slightly reduce the ratio of
free to total halogen and to produce a half-life of
4.8 h. This value is 1.7 times greater than the control
and similar to that produced by cyanuric acid.

DMH photostabilizes chlorine to a greater extent than

cyanuric acid. However, difficulty would occur with the
use of this material in a pool application due to the low
concentrations of free halogen which would be incurred.
DMH produces some photostabilization of HOBr, apparently
by a complexation mechanism, but, the degree of
stabilization is small and no greater than that observed
for cyanuric acid.

E. Glycoluril

Glycoluril was added to both HOCl and HOBr to test its

effect on photolysis (see Table 6). This material
complexed with HOCl producing high total but little free
chlorine. The half-life observed was 24.8 h which is 16
times greater than the control but 1.7 times smaller than
that observed for cyanuric acid. Glycoluril slightly
reduced the ratio of free to total halogen in the HOBr
system. The half-life of bromine decreased to 0.87 h
under these conditions, a destabilization of 3.3 times.
Comparison of this data with that of Nechtman in Table 4
shows a major inconsistency between the two data sets.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 11
December 18, 1989

Glycoluril does not photostabilize chlorine systems as

efficiently as cyanuric acid. Contradictory evidence
exists concerning its function in bromine systems.
Perhaps the order of addition of glycoluril/HOCl/NaBr is
critical. An unknown order of addition was used by
Nechtman. The order of addition in the present studies
was 1) HOC1, 2) NaBr, and 3) glycoluril. If glycoluril
was first mixed with HOCl perhaps the complex formed would
be relatively stable and hence only yield HOBr slowly upon
the addition of NaBr. The glycoluril chlorine system did
produce a strong chlorine complex.

D. Conclusions

The goal of producing a bromine system with a photostability similar to

that of cyanuric acid/chlorine system appears possible. This
conclusion is based on the observation that the dark decomposition rate
of HOBr is slower than the photolysis of cyanuric acid/chlorine
systems.

No bromine system examined to date has produced the same photostability

as that observed for cyanuric acid/chlorine systems. Chlorine systems
are photostabilized by a variety of materials, the order of stability
being DMH > cyanuric acid > glycoluril. Bromine systems are
photostabilized by DMH and cyanuric acid. The effect of these two
compounds is similar with the degree of stability produced being -10
times less than that observed for cyanuric acid/chlorine systems. The
effect of glycoluril on bromine systems is unclear and needs further
characterization.

Two different mechanisms have been postulated for the

photostabilization of halogen systems:

1. Ultraviolet screening, and

2. Photostable complex formation.

Present evidence indicates that the latter mechanism is the one in

operation for all stabilizers reviewed.

Several chemical functionalities in addition to those initially

examined are known to complex halogen, e.g., tertiary and quaternary
amines. In order to thoroughly characterize the relationship between
chemical structure, halogen complexation, and photostabilization, these
materials need to be evaluated.

The analytical methods used to monitor the photostability of HOCl and

HOBr need to be clearly defined and the effects of possible interfering
species such as bromite and bromate described.

In order to correlate lab performance to pool performance simulated

in-pool tests are necessary since factors other than photostability,
i.e., volatility and ammonia complexation are known to influence
halogen stability.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 12
December 18, 1989

E. Recommendations

The following actions are required to determine if a photostable

bromine system can be developed which can compete with cyanuric
acid/chlorine systems on a cost performance basis in outdoor pool
applications.

1. Experimentation to define chemical functionalities which can produce

photostable bromine systems (2.00 man months).

2. Secondary factors which may effect bromine stability are

concentration of bromide and method of bromine generation. Limited
experimentation is necessary to define the importance of these
factors (0.5 man months).

3. Definition and characterization of analytical procedures for

monitoring the proposed halogen decomposition and photolysis
reactions (0.25 man months).

4. The UV-visible spectra of chlorine and bromine systems have

indicated that the spectral range responsible for the majority of
photolysis is 300-350 run. Examination of the UV-visible spectrum of
all materials shown to stabilize halogen systems (0.25 man months).

5. Simulated in-pool tests of the bromine systems showing the highest

stability should be compared with cyanuric acid/chlorine systems to
determine total system stability (1 man month).

6. Preparation of final report (0.5 man months).

The total resources necessary to complete the above experimentation is

4.5 man months. The economic benefits which would be achieved from the
development of a photostable bromine system seems to warrant this
commitment.

The degree of technical risk for this project is medium-high to high.

Hypobromous Acid Photostabilization; a Technical Assessment

Page 13
December 18, 1989

IV. Appendix 1

A. Experimental

Halogen titrations

Several titrometric methods were examined to establish a procedure for

quantitating free and total halogen. The procedures selected for
measuring free and total halogen were the Standard Methods for the
examination of Water and Wastewater Method 408 D procedures al and a3
respectively. The titrations were performed by:

1. Titrating DPD indicator with Ferrous Ammonium Sulfate (FAS) to

obtain the concentration of free halogen
2. Adding 10ml 15% KI, waiting two minutes
3. Titrating the total halogen.

In some cases the Glyco standard analytical method (SAM) R-120

(thiosulfate/KI) was used to determine the total halogen concentration,
but the aforementioned DPD methods were used unless specifically
mentioned otherwise.

UV-Visible Spectra

The UV-visible spectra were obtained on a Perkin Elmer Lambda 4B using

cells of 1 cm path length, distilled water as the reference, a scan
rate of 120 nm/min, and a scan range of 250-400 nm. The concentrations
of the stabilizer solutions examined were 7.75 x 10"3 M (Notebook:
1192-106, 100). The concentration is equivalent to that produced by
1000 ppm of cyanuric acid. This concentration was selected to mimic
the UV filtration effect expected at 20 cm below the surface of pool
containing 50 ppm cyanuric acid. The HOCl solution was prepared by
dilution of "5%" NaOCl solution with distilled water to achieve 8 ppm
as Cl 2 as measured by Kl/thiosulfate (Notebook: (192-174). The HOBr
solution was prepared from the diluted NaOCl solution to which one
equivalent of NaBr was added. The concentration of halogen in the
hypobromous solution was 7 ppm total halogen as Cl 2 by thiosulfate/KI
(Notebook: 1192-133).

Solution Preparation

The standard method for preparing HOCl and HOBr solutions for the dark
decomposition studies and the photolysis studies was as follows. HOCl
solutions were prepared by diluting 0.15 mL "5%" NaOCLwith 1L buffer
solution. The buffer solution was prepared from the dissolution of
21.72 g Na 2 HP0 4 and 13.32g KH2PO4 in 3 L distilled water and
adjusting the pH to 7.4 using 0.5 N KOH. HOBr solutions were prepared
from the addition of 0.01023 g NaBr to the aforementioned HOCl
solutions. This corresponds to 1.1 equivalents of the total halogen
measured in the HOCl solutions. In cases where stabilizers were being
evaluated, stabilizer concentrations of 3.35 x 10~* M were used.^
This concentration corresponds to that produced by 50 ppm cyanuric
acid.
Hypobromous Acid Photostabilization; a Technical Assessment

Page 14
December 18, 1989

Appendix 1 cont.

Dark Decomposition Studies

These experiments were performed by preparing solutions of H0C1 and

HOBr in 1 L volumetric flasks and storing them in the dark over the
duration of the experiment. Periodically aliquots were removed for
%itrat4e.rh _ _ —; __

Photolysis Studies

These studies were performed using a UVA-340 ultraviolet light source

designed to imitate the high energy spectrum of the sun impinging on
the earths surface (300-360 nm). Solutions of HOCl and HOBr were
prepared and 100 ml added to 125 ml jars approximately 5 cm in diameter
and 6 cm high. The jars were covered with filter cells comprised of
4.5 cm diameter, 1 cm high steel rings attached to two 2 mm thick
quartz plates. These filter cells were normally filled with distilled
water but in some cases were filled with materials being examined as UV
absorbers. The covered jars were placed in a constant temperature bath
-9 cm below the UV source.

PGS/jb
 TABLE 1

Hypochlorite Dark Decomposition*

Cl initial Br initial
pH as ppm Cl 2 as ppm Cl 2 t 1/2 of Cl 2 (h)

7.0 3110 0 22

7.0 5 0 1 .37 x 1 0 4 fa

7.0 1 0 6 .85 x 10 4 fa

7.0 2600 637 0 .17

to
7.0 5 1 .2 87
to
7.0 1 0 .25 433

7.9 2700 0 394

7.9 5 0 2 .1 x 1 0 s b

7.9 1 0 1 .1 x 1 0 s b

7.85 2050 573 0 .50

to
7.85 5 1 .4 204
to
7.85 1 0 .28 1020

* Lewin and Avrahami (4)

b
Extrapolated values
 TABLE 2

Hypobromite Dark Decomposition*

Cl initial Br initial
pH as ppm Cl 2 as ppm Br 2 t 1/2 of Br, (h)

"7__Q 0 H4JL. 174

7.9 0 5 606 b

7.9 0 1 3030 b

7.85 2050 573 190

7.85 18 5 2.2 x 1 0 4 b

7.85 3.6 1 1.1 x 1 0 S b

11
Lewin and Avrahami (4)
b
Extrapolated values
 TABLE 3

Halohydantoins
Hydrolysis/Photolysis*

Conditions: pH 7.0, 25°C

light initial free halogen initial total halogen t 1/2; of free t 1/2 of total
Compound present as ppm Cl 2 as ppm Cl 2 halogen (h) halogen (h)

DCDMH No 9.,0 30 .5 3 4

Yes 9..0 30 .5 1 5

DCMEH No 15,.8 34 .0 10 >30

•Yes 15,.0 33 .0 3 20

No 13 .0 25 .8 »30 >30
BCDMH
Yes 13 .0 25 .8 30 6

McFarland (13)
 TABLE 4

Bromine PhotolysisBL , 13

Conditions: pH=7.0 assumed, T=65-80°F

Initial total bromine t 1/2 free bromine t 1/2 total

Glycoluril Initial free bromine bromine (h)
Cone., ppm as ppm Cl 2 as ppm Cl 2 bromine (h)
i
9.,0 1
0 9..0 1
16..0 8.5
25 2.,0 4
17,.0 9
50 1..0 varliable

Nechtman (14)
Br supplied by Ca(OCl)2 + NaBr
 TABLE 5

UV-Visible Spectra, 295-400nm

COTTYDOUnd lamda max (run) Abs (A)

C0-..D.1-
HzO
Succinindde <0.01

Acetamide <0.01
<0.01
DMH
Sustain* <0.01

Cyanuric acid <0.01

Glycoluril 320 0.06

Caffeine <295 2.8 (at 295run)

<295 0.05 (at 295nm)

HOC1

HOBr 330 0.01

Commercial "Algae Shield"

 TABLE 6

H0C1 and HOBr Dark Hydrolysis and Photolysis Studjies

Initial free Initial total
halogen as halogen as free total
Light/ Complexing t 1/2 h t 1/2 h
ppm Cl 2 ppm Cl 2
Halogen Filter Agent Data set
13 1192-169 5.2 5.9 ~10 4 3900
HOC1 Dark
4.4 5.0 185 + 12 189 + 15
HOBr Dark b 1192-170
5.8 6.5 1.48 + 0.10 1.59 + 0.07
HOC1 UV/H2O 1192-182
4.6 5.3 2.63 + 0.05 2.90 + 0.12
HOBr UV/H2O 1192-195
6.3 7.1 53 + 11 41 + 4
HOC1 UV/H2O Cyanuric 1209-9
Acid
4.9 ! 4.9 + 0.6 5.4 + 0.4
HOBr UV/H2O Cyanuric 1209-20 4.3
Acid
6.6 1.8 + 0.04 1.34 + 0.03
HOCl UV/ 1209-31 5.8
Cyanuric Acid
4.8 2.71 + 0.16 2.72 + 0.13
HOBr UV/ 1209-5 4.4
Caffeine
6.7 6 + 3 115 + 32
HOCl UV/H2O DMH 1209-21 0.4
5.5 5.6 + 0.5 4.8 + 0.3
HOBr UV/H2O DMH 1209-22 3.8
6.8 9 + 3 24.8 + 1.4
HOCl UV/H2O Glycoluril 1209-23 0.1
6.1 0.30 + 0.06 0.87 + 0.15
HOBr UV/H2O Glycoluril 1209-25 4.4

- T = 26 + 1°C, pH = 7.40 + 0.05

b
T = 20°C
 REFERENCES

1. Coletta, J, Pacheco, J.F. Project Definition Sheet May 23,

1989.

23, 1989.
3 Jolles, Z.E. "Bromine and its Compounds" New York: Academic
Press, 1966, p. 554-562.
4. Lewin, M.; Avrahami, M. JACS 1955, 77, 4491.
- 5 . ^ g ^ ^ ^ a t o r - L * . S e r l M J t t f i l r H S ^ ^ 7 6 ^
2010.
6. Molina, L.T., Molina, H.J. J- PhyS. Chem. 1978, 82 (22),
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7. Mishalanie, *.*., *ut*o«H.. C.J., Hutte, K.S., Birts, J.W.
J. Phys. Chem. 1986, 90, 5578.
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' ?.&.*'*: ?hys Chem. 1979, 86, 90, 5578.
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14. Neohtnan, J. "Broraine-Glyooluril Stabiliser Screen" Biolab

report 4/25-26/89.
15. Ibid 8/1-10/89.
16. Jolles, Z.E. "Bromine and Its Compounds" New York: Academic
Press, 1966, p. 326, 368, 561.