OKNL /TM- 7 7 88

Contract No. W-7405-eng-26

CHEMICAL TECHNOLOGY DIVISION

AQUEOUS CHEMISTRY OF CHLORINE: CHEMISTRY, ANALYSIS,

AND ENVIRONMENTAL FATE OF REACTIVE OXIDANT SPECIES

R. L. J o l l e y
J. H. Carpenter*

Date P u b l i s h e d - January 1982

NOTICE This document contains information of a preliminary nature.

I t is subject to revision or correction and therefore does not represent a
final report

*Rosenstiel School of Marine and Atmospheric Science, University

of M i a m i , Miami, Florida 3 3 1 4 9 .

OAK RIDGE NATIONAL LABORATORY

Oak Ridge, Tennessee 37830
o p e r a t e d by
UNION CARBIDE CORPORATION
for the
DEPARTMXNT OF ENERGY

3 4456 0 3 2 2 L b 9 9

.. .,.....
 Jii

CONTENTS

E322
LISTOFFIGURES ........................ v

LISTOFTABLES ........................ vii

ACKNOWLEDGEMENTS . . . . . . . . . . . . . . . . . . . . . . . . ix

ABSTRACT . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1

1. INTRODUCTION . . . . . . . . . . . . . . . . . . . . . . . . 2

2. AQUEOUS CHEXISTRY OF CHLORINE. . . . . . . . . . . . . . . . 3

2.1 Free Oxidant Chemistry. . . . . . . . . . . . . . . . . 7

2.2 Combined Oxidant Chemistry. . . . . . . . . . . . . . . 13
2.3 Chlorine Demand . . . . . . . . . . . . . . . . . . . . 30

3. ANALYTICAL METHODS FOR OXIDANT SPECIES TN

CHLORINATED WATERS ..................... 39

3 . I General Analytical Considerations . . . . . . . . . . . 41

3 . 2 Potentiometry . . . . . . . . . . . . . . . . . . . . . 46
3 . 3 Amperometry . . . . . . . . . . . . . . . . . . . . . . 49
3.4 Spectrophotometry . . . . . . . . . . . . . . . . . . . 52
3 . 5 Colorimetry . . . . . . . . . . . . . . . . . . . . . . 52
3 . 6 Chemiluminescence . . . . . . . . . . . . . . . . . . . 62
3.7 Titri-metry. . . . . . . . . . . . . . . . . . . . . . . 63
3 . 8 Comparative Studies . . . . . . . . . . . . . . . . . . 70
3 . 9 Summary of Analytical Methods . . . . . . . . . . . . . 82

6. ENVIRONMENTAL FATE . . . . . . . . . . . . . . . . . . . . . 89

4 . 1 Freshwater System . . . . . . . . . . . . . . . . . . . 91
4.2 S a l i n e Water System . . . . . . . . . . . . . . . . . . 94
4 . 3 Distribution and Transport. . . . . . . . . . . . . . . 96

5. REFERENCES . . . . . . . . . . . . . . . . . . . . . . . . . 99
 V

L I S T OF FIGURES

Figure Page

1 Schematic outline of chemical reactions in

freshwater, estuarine, and marine waters
(Sugam and Helz, 1980) .............. 4
Graphic description of the breakpoint
phenomenon . . . . . . . . . . . . . . . .. . . . 18

Principal species of bromine and bromamine

predominating a f t e r 1 to 2 min at various
pH and ammonia-to-bromine ratios .....
4 Principal chemical pathways f o r reaction,
degradation, and environmental fate of free
chlorine in the aquatic environment. ....... 90
 vii

LIST OF TABLES

Table

1 Free oxidant reactions: principal reactions oE

environmental concern for chlorine in aqueous
solutions ....................... 6

2 Distribution of principal oxidizing species for

aqueous chlorine solution at 15°C (Morris, 1978a) ... 8

3 Distribution of principal oxidizing species of

bromine produced by chlorination of bromide in
natural waters at 25°C as a function of pH and
bromide content .................... 12

4 Proportions of monochloramine (NH2C1) and di-

chloramine (NHC12) formed at equilibrium conditions
in water chlorination with equimolar concentrations
of chlorine and ammonia as a function of temperature
and pII (data selected from S a f e Drinking Water
Committee, 1980). ................... 16

5 Precision and limit of detection of analytical

methods f o r determining free chlorine (Nicolson,
1965). ........................ 72
Analysis of Analytical Reference Service Water
Chlorine (Residual) No. 1 (Sol10 et al., 1970). .... 74
Comparison of analytical methods for determining
free and total chlorine in aqueous solution con-
taining 0.98 m g / L free chi-orine (Tdshka and
....................
McFarren, 1 9 7 1 ) 76

8 Comparison of analytical methods for determining

total chlorine in aqueous solution containing 0.66
mg/L total chlorine (Lishka and McFarren, 1981) .... 77
Determination of total chlorine in drinking water
9
(Bender, 1978). .................... 78

10 Determination of total chlorine in river water

(Bender, 1978). .................... 79

11 Determination oE total chlorine in secondary

effluent from wastewater treatment plant (Bender,
1978). ........................ 80

12 Chlorine concentration in seawater (measured by

six different experimentalists and five different
methods), ....................... 83
 viii

LIST OF TABLES

Table

13 Summary of applicability of analytical methods f o r

available chlorine (free and combined oxidant species).
For definition of lower limits of detection, see
Sect.3.1.1 ...................... 84

14 Concentration of active halogen species for chi-ori-

.............
nation of freshwater ( m o l / T , ) . 93

15 Concentrations of active halogen species in a test

.......
case f o r chlorination of seawater ( m o l / L ) 97
 ix

ACKNOWLEDGEMENTS

T h i s report was prepared in partial fulfillment of Interagency

Agreement EPA-79-D-X0789 by the Oak Ridge National Laboratory under the
sponsorship of the Environmental Protection Agency. A major objective
of the agreement was to assist in the preparation of critical reviews
of the chemical and environmental fates of chlorine in aquatic environ-
ments and analytical methodology €or chlorine OK oxidant analysis. The
reviews provide part of the information base for a criterion document
on the human and environmental effects of chlorine in fresh and marine
waters. We express our appreciation to W. A . Rrungs for making this
project possible.

We acknowledge further the efforts of the following: M. R. Bennett,

W. J. Cooper, W. R. Haag, 1,. H. Howe, J. D. Johnson, C. E. Lamb, M. H.
Lietzke, R. A. Minear, R. Sugam, and H. E. Zittel f o r critically review-
ing this report; C. H. Shappert for editing the manuscript; D. K. Jolley
for typing assistance; S. R. Damewood for the typing of several drafts;
and B. H. Laughlin f o r the typing of the final manuscript.
 1

AQUEOUS CHEMISTRY OF CHLORINE: CHEMISTRY, ANALYSIS,

mD ENVIRONMENTAL FATE OF REACTIVE OXIDANT SPECIES

R. L. J o l l e y
J . H. C a r p e n t e r "

ABS TRACT

C h l o r i n e i s used e x t e n s i v e l y as a b i o c i d e f o r t r e a t m e n t of d r i n k i n g
water, w a s t e w a t e r , and c o o l i n g water. The c h l o r i n a t e d w a s t e w a t e r s and
p r o c e s s waters d i s c h a r g e d t o a q u a t i c e c o s y s t e m s can c o n t a i n r e a c t i v e
c h l o r i n e s p e c i e s and c h l o r i n e - p r o d u c e d o x i d a n t species. The e n v i r o n -
m e n t a l f a t e and p o s s i b l e h a z a r d s a s s o c i a t e d w i t h t h e s e c h e m i c a l compounds
are of much p u b l i c c o n c e r n . T h i s r e p o r t r e v i e w s (1) t h e c h e m i s t r y of
c h l o r i n e r e l a t i v e t o i t s r e a c t i o n s i n f r e s h , e s t u a r i n e , and marine waters
and t h e f o r m a t i o n of r e a c t i v e o x i d a n t s p e c i e s ; ( 2 ) t h e c u r r e n t s t a t u s
of c h e m i c a l a n a l y s i s of r e a c t i v e c h l o r i n e s p e c i e s and c h l o r i n e - p r o d u c e d
o x i d a n t s p e c i e s r e l a t i v e t o a n a l y s i s of low c o n c e n t r a t i o n s (microgram-
p e r - l i t e r r a n g e ) and d e t e r m i n a t i o n of a c c u r a c y and p r e c i s i o n of methods;
and ( 3 ) t h e e n v i r o n m e n t a l f a t e of c h l o r i n e and c h l o r i n e - p r o d u c e d o x i d a n t
species.

The n a t u r e and c o n c e n t r a t i o n s of r e a c t i v e c h l o r i n e species and

c h l o r i n e - p r o d u c e d o x i d a n t species formed i n c h l o r i n a t e d w a t e r s are a
f u n c t i o n of t h e c h l o r i n e dosage and c h e m i c a l c o m p o s i t i o n o f t h e w a t e r
[ e . g . , pH, t e m p e r a t u r e , ammonia c o n c e n t r a t i o n , s a l i n i t y , o r g a n i c con-
s t i t u e n t s (such as o r g a n i c - n i t r o g e n compounds), i n o r g a n i c c o n s t i t u e n t s
( s u c h as bromide o r manganese), and p r e s e n c e of s u n l i g h t ] . The e f f e c t s
of t h e s e v a r i a b l e s on c h l o r i n e and o x i d a n t s p e c i a t i o n are d i s c u s s e d .

A l a r g e number of a n a l y t i c a l methods are a v a i l a b l e f o r d e t e r m i n i n g

c h l o r i n e o r o x i d a n t species i n water. The methods a r e grouped and d i s -
cussed i n t h e following categories: (1) d i r e c t p r o p e r t y measurement
( p o t e n t i o m e t r y , amperometry, and s p e c t r o p h o t o m e t r y ) ; ( 2 ) c o l o r i m e t r y ;
(3) chemiluminescence; and ( 4 ) t i t r i m e t r y . A p r i n c i p a l o b j e c t i v e of
t h i s r e v i e w of a n a l y t i c a l methods w a s t o p r o v i d e c o m p a r a t i v e d a t a t o
p e r m i t a s s e s s i n g t h e s i g n i f i c a n c e of c h l o r i n e species a n a l y s e s r e p o r t e d
i n t o x i c i t y data.

The u l t i m a t e d e c o m p o s i t i o n p r o d u c t s o f f r e e c h l o r i n e i n n a t u r a l .
water are c h l o r i d e , o x i d i z e d o r g a n i c s , c h l o r o o r g a n i c s , oxygen, n i t r o g e n ,
and p o s s i b l y c h l o r a t e and n i t r a t e . Depending on t h e bromide c o n t e n t of
t h e c h l o r i n a t e d w a t e r s , o t h e r p o s s i b l e p r o d u c t s are bromate and bromo-
o r g a n i c s . The e n v i r o n m e n t a l f a t e of c h l o r i n e i n n a t u r a l waters i n v o l v e s
sets of complex r e a c t i o n s t h a t are i n t e g r a t e d i n t o a c o n c e p t u a l model.

--.
" R o s e n s t i e l School of Marine and Atmospheric Science, U n i v e r s i t y o f
M i a m i ; M i a m i , F l o r i d a 33149.
 2

1. TNTROD[JCTTON

C h l o r i n e i s commonly used as a w a s t e w a t e r d i s i n f e c t a n t and an a n t i -

f o u l i n g a g e n t f o r c o o l i n g water s y s t e m s . The b i o c i d a l and a n t i f o u l a n t
c a p a b i l i t i e s of c h l o r i n e are a f u n c t i o n of t h e r e a c t i v e c h l o r i n e and
o x i d a n t s p e c i e s produced i n c h l o r i n a t e d water. Much e v i d e n c e i n d i c a t e s
t h a t e f f l u e n t s c o n t a i n i n g r e a c t i v e c h l o r i n e s p e c i e s , chlorine-produced
o x i d a n t s p e c i e s , and r e a c t i o n p r o d u c t s may he t o x i c t o a v a r i e t y of b i o -
l o g i c a l s p e c i e s i n t h e r e c e i v i n g waters. C o n s e q u e n t l y , an u n d e r s t a n d i n g
o f t h e f o r m a t i o n and e n v i r o n m e n t a l f a t e of t o x i c s p e c i e s and r e a c t i o n
products, i n a d d i t i o n t o t h e i r t o x i c i t y , is necessary t o e s t a b l i s h l i m i t s
r e g a r d i n g c h l o r i n a t i o n of wastewater and c o o l i n g w a t e r e f f l u e n t s .

Thi.s r e p o r t ; r e v i e w s t h e c h e m i s t r y of c h l o r i n e r e l a t i v e t o t h e f o r m a t i o n
and d e g r a d a t i o n of r e a c t i v e c h l o r i n e s p e c i e s , c h l o r i n e - p r o d u c e d o x i d a n t
s p e c i e s , and r e a c t i o n p r o d u c t s i n f r e s h , e s t u a r i n e , and m a r i n e waters.
The a n a l y t i c a l methods f o r c h l o r i n e and o x i d a n t s p e c i e s are p r e s e n t e d i n
d e t a i l w i t h two p r i n c i p a l . o b j e c t i v e s , namely: (1) d e t e r m i n a t i o n of t h e
a c c u r a c y and p r e c i s i o n of t h e methods t o assist i n e v a l u a t i o n of t o x i c i t y
d a t a , and ( 2 ) d e t e r m i n a t i o n of t h e s e n s i t i v i t y and r e l i a b i l i t y of t h e
methods r e l a t i v e t o a n a l y s i s of low c o n c e n t r a t i o n s of c h l o r i n e and o x i d a n t
species. The e n v i r o n m e n t a l f a t e of t h e c h l o r i n e and o x i d a n t s p e c i e s i s
d i s c u s s e d w i t h r e s p e c t t o t i m e and c o n c e n t r a t i o n .
 3

2. AQUEOUS CHEMISTRY OF CHLORINE

The aqueous chemistry of chlorine with respect to chlorination of

water and wastewater has been reviewed by several investigators (Hall
et al., 1981; Jolley, 1 9 7 3 , 1 9 7 8 ; Jolley et al., 1978b, 1980; McKee
et a l . , 1960; Morris, 1975, 1978a, 1978b; Opresko, 1980; Safe Drinking
Water Committee, 1980; and White, 1972). The following review summarizes
the chemistry of chlorine relevant to the discharge of chlorinated waters
and wastewaters t o the environment.

When pure water is chlorinated, the principal chlorine-containing

species excluding chloride ion are chlorine ( C l z ) , hypochlorous acid
(HOCl), and hypochlorite ion (OC1-). If ammonia is present in the water
undergoing chlorination, chloramines are also formed. Monochloramine
(NH2C1), dichloramine ( N H C 1 2 ) , and nitrogen trichloride ( N C 1 3 ) may b e
present. The types and quantities of molecular species present are de-
termined by the reactant concentrations, reaction rates and equilibria,
pH, and temperature, Bromide and iodide, if present even at l o w concen-
trations, are oxidized by chlorine forming oxidation products such as
hypobromous acid (HOBr) and iodine (12). Hypobromous acid may, in turn,
react with ammonia, if present, to form bromamines analogous to chlor-
amines. Bromine and iodine-containing oxidants become increasingly sig-
nificant with increasing bromide and iodide concentrations ( e . g . , in
estuarine and marine waters). Sugam and H e l z (1980) have schematically
summarized these chemical reactions of chlorine in freshwater and seawater,
as shown in Fig. 1. This diagram indicates in a simplified fashion the
complex interrelationship of the reaction pathways.

Chlorine present in aqueous solution as hy-pochlorous acid and hypo-

chlorite ion is called '@freechlorine" (free residual chlorine). Although
generally of little consequence in waters at near-neutral pH values,
molecular chlorine and nitrogen trichloride are also usually analyzed as
f r e e chlorine. Chlorine present as monochloramine ( N H 2 C 1 ) , dichloramine
(NHClZ), and organic N-chloro-compounds in which the chlorine-containing
compound has a lower oxidation potential than free chlorine is called
"combined chlorine" (combined residual chlorine). Nitrogen trichloride
 4
‘L ‘L
ai ai
 5

(NC13), although analytically usually appearing as free chlorine, is de-

fined as combined chlorine. "Total chlorine" (total residual chlorine)
is the sum of the free and combined chlorine.

Hypobromous acid and hypoiodous acid are detected by the usual

analytical methods as free chlorine. HOBr will also react with ammonia
t o produce bromamines that are also detected as free chlorine. Thus the
terms "free oxidant" and "combined oxidant'' are more appropriate than
free chlorine and combined chlorine when solutions containing bromide or
iodide (e.g., seawater) are the subject of analysis. However, present
analytical methods may not differentiate between free and combined bromine
species.

Analytical results are customarily reported as nominal chlorine mass

units (e.g., as mg/L chlorine). Hall et al. (1981) believe a convenient
and more general unit is microequivalent per liter or micronormality ( u N )
particularly when chemical reactions are considered.

The possible chemical reactions of chlorine in aqueous solution are

quite varied and complex. The major types of reactions are given in Table
1. Compilations of thermodynamic, equilibrium, and kinetic data for many
reactions of concern have been made by Lietzke (1978), Haag and Lietzke
(1980), and Hall et al. (1981). These scientists and others (e.,q..
Sugam and Helz, 1980) are making significant efforts to integrate water
quality data with known kinetic and equilibrium data for the possible
chemical reactions in order to predict the products of the chlorination
of natural waters. Such computer programs and models shou3.d facilitate
a more thorough understanding of both chlorination products and their ulti-
mate fate and distribution.

The major objective of this report is to review the chemistry of

chlorine in wastewaters and natural waters (fresh and marine) as it per-
tains to the formation, degradation, and reaction products of f r e e and
combined oxidants. Thus it deals principally with the inorganic chemistry
of chlorine and oxidant products that are environmentally correlated with
acute toxicity. A major aspect of the chemistry of chlorine or chlorine-
produced oxidants is that dealing with the many possible organic reactions
 6

TaR1.e 1. Free oxidant reactions: principal reactions of

environmental concern f o r chlorine in aqueous s o l u t i o n s "
__I .
-..
...
...
..I
.-. .........._III__ ..........I_.

Reaction type Examp le

II_ 111

Water C12 + E120 = HOC1 + HCl

Ammonia

Substitution NH3 +- HOC1 + Nl12C1 -k H z O

Ox id a 1: ioil 2 N H C 1 2 -1- H 2 0 -f N2 + HOC1 I- 311" + 3C1-

Inorganic. oxidation Mn2+ I- HOC1 + 2H2O -). MnO(OH)2 -I- 31%

f
+ C1-

Disproportionation 30C1" 2Cl- + CI03

I

Decomposition 2HOC1 -+ 2H+ f 2 C 1 " I- 0 2

Organic reactions

Oxidation RCHO -I- HOC1 -+ RCOOH I- HI- + C1-

Add i t i o n RC=CR' +- E I O C ~ -t RC(OH)C(C~)R'

Substitution

N - C 1 bond FWiz I- HOC1 + RNHCI. 4. 820

c-c1 RCOCH3 + 3HOC1 3 RCOOH 3- H C C l 3 4- 2H20

-~

"Analogous reactions may occur for bromine and iodine by-products

of w a t - e r chlorinat i.on.
 7

and reaction products; however, it is mentioned only very briefly because

it was not within the specified scope of this review. Although the ulti-
mate environmental 'Isink'' or fate of chlorine as "
C
1
'
" is C1-, haloorganics
and oxidized organics play a role of considerable importance in the re-
actions and degradation of chlorine. Indeed, haloorganics and/or oxidized
organic products may be associated with possible long-term chronic toxic
effects of chlorine reactions in natural waters and, consequently, of some
environmental significance.

2.1 Free Oxidant Chemistry

2.1.1 Chlorine chemistry

Chlorine gas hydrolyzes very rapidly in water according to the follow-
ing reaction:

C12 + H20 = HOCl + 4-

H + Cl- . (1)
The hydrolysis constants for this reaction range from 1.5 x l o M 4 at O°C to
4.0 x at 25OC (Connick and Chia, 1959; Morris, 1978a). The forward
rate constant i s 13.7 s-l at 2S°C,indicnting a reaction half-life for Cl2
of 0.05 s (Hall e t al., 1981). Morris (1966, 1978b) concluded that
for normal conditions of chlorination of fresh water and wastewater, the
hydrolysis is essentially complete at pH values >6. While Morris made
calculations for "seawater," he neglected the ionic strength effects and
the reaction of chlorine with bromide so that the values have relatively
little applicability to actual seawater (Carpenter, 1978).

Hypochlorous acid is a weak acid. It dissociates or ionizes with a

dissociation constant ranging from 1.6 x at 0°C to 3 . 2 x at
25°C (Morris, 1966). At pH 7.5 and 25OC, HOC1 and OC1- are equimolar in
concentration.

HOCl = H
++ OCl- .
At higher pH, O C l - becomes the major form of chlorine and at l o w e r pH,
HOCl becomes dominant. Morris (1978a) calculated the distribution of
principal. oxidizing species for aqueous solutions at 15°C as a function
of pH and chloride concentration (Table 2). These equilibria are important
because the toxicity and/or reactivity depend on the particular chemical
 8

Table 2. D i s t r i b u t i o n of p r i r i c i p a l o x i d i z i n g s p e c i e s f o r
aqueous c h l o r i n e s o l u t i o n at 1 5 ° C (Morris, 1 9 7 8 a )

F r a c t i o n o f ...o...x
...i d i z i n g c h l o r i n e
(21.2 HOC1 0c1-

2” 3.6 x 0.997 0.003

2a 3.6 10-5 0.975 0.025

2a 2 . 9 x low6 0.797 0.203

2a 1 . 0 x 10-7 0.280 0.720

2a 1.0 1.0-9 0.038 0.962

a
F r e s h w a t e r , c h l o r i d e at: 350 mg/T.. .
 9

species present. The fraction of molecular C12 is a very small fraction

of the total oxidizing chlorine, but this does not necessarily preclude
its involvement in reactions or disinfection. Vapor transport of molecular
C12 is insignificant at low concentrations of chlorine and neutral pH
values. However, at acidic pH values and high concentrations of chlorine
(e.g., pH 2 and 3500 mg/L chlorine), an appreciable amount of molecular
C12 is present, and vapor transport of molecular C12 may become significant
(White, 1972). Other possible transient oxldizing species are principally
of academic interest.
+ would
For example, H 2 0 C l be present only at ex-
tremely low concentration at pH 5 to 9 (Safe Drinking Water Committee,
1980). It is probably the species responsible f o r acid catalysis of many
reactions of HOC1 (Morris, 1978a).

Hypochlorite solutions. If sodium or calcium hypochlorite are used

as the source of active aqueous chlorine, they provide hypochlorite ions
as follows:

The hypochlorite ion very rapidly establishes equilibrium with hypochlorous

acid [see reaction ( 2 ) ] . Thus at the same pII and temperature, the compo-
sition of the aqueous solution is the same whether starting with chlorine
gas or a hypochlorite (Morris, 1978b).

Although hydrolysis of chlorine gas (reaction 1) produces hydrogen

ions thus tending to lower the p H , and dissolution of hypochlorite con-
sumes hydrogen ions in r e a c h i n g equilibrium [reactions (2), ( 3 ) , and ( 4 ) ] ,
thus tending to raise the pH, the pH effect is generally very small at the
lower milligram-per-liter concentrations o f chlorine used in water and
wastewater treatment (Morris, 1978b). However, in the immediate vicinity
of the injection of strong solutions of chlorine or hypochlorite, the pH
change may b e very significant.

2.1.2 Bromine chemistry

If bromide is present as in some freshwaters, brackish waters, and

seawater, the added chlorine will oxidize the bromide rapidly (Farkas
 10

e t a l . , 1.949) as f o l . 1 . 0 ~ ~ :

HOCl + Br- +. H O B r 4 C1- . (5)

The r a t e c o n s t a n t f o r t h i s r e a c t i o n i s pH d e p e n d e n t , s i n c e O C l - does
not oxidize Br- a t n e a r l y t h e rate t h a t HOCl does:

where Ka i s t h e i o n i z a t i o n c o n s t a n t f o r HOC1.

The r a t e c o n s t a n t f o r r e a c t i o n ( 5 ) i s 4.7 x exp(-754.9/T) L

rno1-l s-l, where r i s i n K e l v i n u n i t s (Inman and Johnson, 1 9 7 9 ) . For
seawater w i t h a n a t u r a l bromide i o n c o n t e n t of 65 rng/T, and pII of 8 , t h e
r a t e c o n s t a n t would b e 1 4 1 1, mol-’ s-’ a t 25°C (Haag and L i e t z k e , 1 9 8 0 ) .
Hall e t a l . (1981) r e p o r t c o m p u t a t i o n s t h a t t h e r e a c t i o n i n s e a w a t e r
i s complete i n a p p r o x i m a t e l y 10 s .

I n p u r e aqueous s o l u t i o n s , the c h e m i s t - r i e s of bromine and c h l o r i n e

show q u a l i t a t i v e s i m i l a r i t i e s . The primary bromine s p e c i e s are m o l e c u l a r
bromine ( R r z ) , hypobromous aci.d (WOBr) and hypobromite i o n (OBr-). The
e q u i l i b r i a between t h e s e s p e c i e s a r e c o n t r o l l e d by t h e f o l l o w i n g r e a c t i o n s :

B r 2 4- H 2 0 = I l O B r + H+ + Br-, I$, = 5.8 x a t 25°C ; (7)

IIOBr = O B r - -1- 11
-+-, K = 2 x lo-’ at 25°C (8)
a
~

A primary d i f f e r e n c e between t h e c h l o r i n e and bromine s y s t e m s i s

t h a t t h e r e i s a r e l a t i v e l y h i g h c o n c e n t r a t i o n of mo1.ecula-c R r 2 a t n e a r
n e n t r a l pH v a l u e s compared w i t h v e r y low c o n c e n t r a t i o n s of mol.ecular C l z
(LaPointe e t n l . , 1975). A second i m p o r t a n t d i f f e r e n c e i s t h a t f o r a
g i v e n pH v a l u e , H O B r i o n i z e s t e n f o l d less t h a n H O C l d o e s . S i n c e t h e un-
i o n i z e d forms are more e f f e c t i v e i n d i s i n f e c t i o n or b i o f o u l i n g c o n t r o l ,
s y s t e m s t h a t c o n t a i n bromide i.on w i l . 1 r e s p o n d v e r y d i f ferent:J-y t o any
p a r t i c u l a r c h l o r i n a t i o n dosage.

While bromine and bromide i o n can form t r i b r o m i d e i o n , the e q u i l i b -

rium c o n s t a n t i s about 1 5 . 9 a t 25°C. Thus i n n a t u r a l w a t e r s , i n c l u d i n g
seawater w i t h a bromide c o n c e n t r a t i o n of 65 rng/L, t h e f o r m a t i o n of
 11

tribromide is insignificant. The relative fraction of Br2 and HOBr can

be calculated from the following relationship (Safe Drinking Water Com-
mittee, 1980):

(Br2)
log - -
(HOBr)
= log (Br-) - pH f 8.24 .
Hypobromous acid is a weak acid with a dissociation constant of
2 x at 2 5 O C (see reaction ( 6 ) ; Farkas and Lewin, 1950). At pH 8 . 7
and 25"C, HOBr arid OBr- are present in equimolar concentrations. At
higher pH, OBr- becomes the major form of bromine; at Lower pR, HOBr
becomes dominant (Tab1.e 3 ) . Lower temperature increases the pH range
where HOBr is the dominant species. A t pH values <6, halide species such
as B r 3 - and B r C l may be present. However, these are n o t significant at
the pH o f natural waters (Hall et al., 1981).

The distribution of chemical species of bromine given in Table 3

were calculated from the equilibrium constants for the hydrolysis of
bromine and dissociation of hypobromous acid, The principal reactive
bromine species in chlorinated freshwater is probably HOBr at neutral
pH. In seawater, HOBr is probably the most reactive species, although
a significant fraction is made up of molecular bromine because of the
r e l a t i v e l y high concentration of bromide tending to displace the equi-
librium of reaction (7) toward the left.

2.1.3 Iodine chemistry,

The reaction of H O C 1 with iodide is very rapid (Lister and Rosenblum,

1963) :

HOC1 f I- f HOI + C1- . (10)

Molecular iodine (I?) exists in equilibrium with the R O I oxidation product

0.f free chlorine.

I2 4- H20 = HOI 1- H
+f 1- . (11)

'The equilibrium constant for this reaction is 5.44 x at 25OC (Burger

and Liebhafsky, 1 9 7 3 ) . The average concentration of iodine in freshwater
is estimated as 2 vg/L and that in seawater as 60 v g / L (Sengupta et al.,
1978). The presence of N O 1 i n some chlorinated freshwaters is shown by
 1.2

Tab1.e 3. D i s t r i b u t i o n of p r i n c i p a l o x i d i - z i n g s p e c i e s of bromine
produced by c h l o r i n a t i o n of bromide i n n a t u r a l w a t e r s a t 25°C
as a f u n c t i o n of pW and bromide c o n t e n t

-
. ._ P e r c e n t a g e of bromine species ... .
Bromide Bromide
b
.- (65 %.lT.)___
PB Br2 HOBr OBr- Br2 HOBr OBr”

5 3 10-3 100 0.02 32 68 0.01

6 3 x 100 0.2 4.6 95 0.2

7 3 10-~ 98 2 0.05 98 2

7.8 - - - 0.04 89 11

8 3 x 10-6 83 17 0.04 83 17

9 3 33 67 2 10-3 33 67

10 3 x 10-8 5 95 2 10-5 5 95
nAssumed c o n c e n t r a t i o n f o r f r e s h w a t e r s based on molar ratio of
bromide t o c h l o r i d e i n seawater ( 1 . 6 x and assuming c.hl.oride
c o n c e n t r a t i o n of 10 mg/L i n f r e s h w a t e r ,
b
Approximate c o n c e n t r a t i o n o f bromide i n seawater.
 13

the formation of dichloroiodomethane in many drinking waters (Thomas

et al., 1980). In oxygenated seawater, iodine is probably present as
iodate (Wong and Brewer, 1977) and relatively unreactive (thermo-
dynamically stable) (Safe Drinking Water Committee, 1980).

The dissociation constant, Ka, for the dissociation of HOT [ E q . (12)]

at 2 O o C is 4.5 x (Safe Drinking Water Committee, 1980). The dissoci-
ation of H O I is expressed as

HOI = H
+ + 01- . (12)
A t p H 7 , the concentration of H O I is about l o 5 greater than 01-, and at
p H 7.8 (seawater) the concentration of H O I is l o 4 greater than 01-. Thus
the dissociation of H O I occurs only at a high pH and is not of practical
significance in the chlorination of natural waters and wastewaters. About
pH 9, H O I disproportionates rapidly to iodate and iodide (Safe Drinking
Water Committee, 1980):

3HOI + 20H- -f HIO3 + 21- + 2H20 . (13)

2.2 Combined Oxidant Chemistry

2.2.1 Chloramines

Hypochlorous acid (HOC1) reacts rapidly with ammonia to form mono-

chloramine ( N H 2 C 1 ) , dichloramine ( N H C l z ) , or nitrogen trichloride ( N C I ?)

as shown in reactions ( 1 4 ) through (161,

NH2C1 + HOC1 = N H C 1 2 + H20 , (15 i

The reaction products are dependent upon the pH, the relative concen-
trations of hypochlorous acid and ammonia, the reaction time, and the
temperature (Morris, 1978b).

Usually monochloramine is the only chloramine that is observed (1)

when pH values are ' 8 , and (2) when the molar ratio of hypochlorous acid
to ammnnia is 51.0. At higher chlorine-to-ammonia ratios or at lower pH
values, dichloramine and trichloramine (also called nitrogen trichloride)
 14

are formed, A t pH v a l u e s < 3 , o n l y n i t r o g e n t r i c h l o r i d e i s o r d i n a r i l y

d e t e c t e d ( M o r r i s , 1978b). These and o r g a n i c c h l o r a m i n e s are produced
d u r i n g t h e c h l o r i n a t i o n of w a t e r c o n t a i n i n g ammonia o r o r g a n i c amines
T h e i r p r e s e n c e may c o n t r i b u t e t o t a s t e and odor problems i n f i n i s h e d
d r i n k i n g water (Symons e t a l . , 1 9 7 5 ) .

Drago (1957) d e s c r i b e d t h e g e n e r a l c h e m i s t r y of monochloramine, and

'I'heilaeker and Wegner (1964) and Kovacic e t al. (1970) r e p o r t e d i t s o r -
g a n i c r e a c t i o n s i n some d e t a i l . Most of t h e s e 0rgani.c r e a c t i o n s o c c u r r e d
i n nonaqueous media. Although e x t r e m e l y u s e f u l f o r o r g a n i c s y n t h e s e s ,
t h e s e experi-ments have o n l y l i m i t e d val.ue € o r p r e d i c t i n g r e a c t i o n s t h a t
may o c c u r i n c h l o r i n a t e d water.

Monochloramine h a s been t h e p r i n c i p a l s u b j e c t o f s e v e r a l reviews.

Its p r o p e r t i e s and c h e m i s t r y have been d e s c r i b e d by Metcalf (1942), Colton
and J o n e s (1955), J a n d e r ( 1 9 5 5 a ) , Drago (1957), T h e i l a c k e r and Wegner
(1964), Czech e t a l . (19611, Gmelin (1969), and Kovacic e t a l . (1970).
Monochloramine i s a c o l o r l e s s , w a t e r - s o l u b l e liquid with a freezing point
of -66°C. I t may decompose v i o l e n t l y above t h a t t e m p e r a t u r e .

R e l a t i v e l y l i t t l e i s known a b o u t d i c h l o r a m i n e , Chapin (1929) d e t e r - -

mined t h a t i t s o d o r , v o l a t i - l i t y from aqueous s o l u t i o n , and relat.i.ve s o l u -
b i l i t y i n v a r i o u s s o l v e n t s a r e i n t e r m e d i a t e between t h o s e of monochloramine
and n i t r o g e n t r i c h l o r i d e e Be a l s o found t h a t diclilwramine l i b e r a t e s
i o d i h e from a c i d i f t e d p o t a s s i u m i o d i d e ( K l j s o l u t i o n a s d o t h e o t h e r
chloramines. Dichloramine s o l u t i o n s are r e p o r t e d t o be u n s t a b l e ( C o r b e t t
et al. ~ 1953). Recentl-y, G r a y e t a l . , (1978) r e p o r t e d t h a t aqueous d i -
c h l o r a m i n e s o l u t i o n s are more s t a b l e t h a n p r e v i o u s l y t h o u g h t and, t h u s ,
may b e more s i g n i f i c a n t i n water t r e a t m e n t p r o c e s s e s .

N i t r o g e n t r i c h l o r i d e i s a b r i g h t yel.l.ow l i q u i d w i t h a s t r o n g i r r i -
t a t i n g odor and l a c h r y m a t o r y fumes. I t s m e l t i n g p o i n t i s below -40°C;
i t s b o i l i n g p o i n t i s 70°C. It i s e x t r e m e l y e x p l o s i v e a n d , t h e r e f o r e ,
dangerous, except a t very l o w c o n c e n t r a t i o n s . Its s o l i i b i l i t y i n w a t e r
is l i m i t e d . I n aqueous s o l . u t i o n s i t decomposes s l o w l y t o ammon-i.a and
hypochlorous a c i d (Remick, 1 9 4 2 ) . The h y d r o l y s i s r e a c t i o n i s pH depen-
d e n t (Koscher et: a l . , 1 9 8 0 ) . C o r b e t t e t a l . (1953) o b s e r v e d t h a t aqueous
 15

solutions of nitrogen trichloride are stabilized by small amounts of acid.

The compound is an effective chlorinating agent, particularly in non-
aqueous media (Dowell and B r a y , 1917; Houben and Weyl, 1962; Jander, 1955b;
Kovacic et al., 1970).

Monochloramine is the principal chloramine that is encountered under

the usual conditions of water and wastewater chlorination. The rate of its
formation, shown in reaction (141, is extremely rapid at the concentrations
and conditions of water treatment. At the pH range of most water and waste-
waters, the reaction is usually 90% complete In ~1min. The reaction rate
is maximum at pH 8.5 (Morris, 197%; Weil and Morris, 1949). The reaction
rate constant for the formation of monochloramine, assuming reaction be-
tween neutral molecules is 5.6 x lo6 L mol-’ s-’ at 20°C (Saguinsin and
Morris, 1975).

The specific rate of formation of dichloramine is much slower than

that for monochloramine except at pH values 15.5 (Morris, 1978b). The
reaction rate constant for t h e formation o f dichloramine is 2.7 x lo2 L
mol-’ s-l at 20°C (Saguinsin and Morris, 1975). The relative ratio of
monochloramine and dichloramine is a function of the reaction kinetics.
Because dichloramine forms much more slowly than monochloramine at near-
neutral pH values, dichloramine does not constitute a large percentage
of the available chlorine unless the waters are quite acid o r when the
molar ratio of chlorine to ammonia is pl. Assuming equilibrium conditions,
the relative proportion of dichloramine and monochloramine for equimolar
chlorine and ammonia from pH 4 to 9 a r e shown in Table 4 .

At pH values of 5 o r less, monochloramine is slowly converted to

dichloramine (Morris, l978b) ,
+
2NtI2C1 + H+ -f NHC12 + NH4 . (17)
Dichloramine is much less stable than monochloramine or nitrogen tri-
chloride. The decomposition of dichloramine is simplified in reaction
(18). The actual reaction is more complicated: more chlorine is reduced
and some nitrate is formed (Morris, 1978b).

2NHC12 + H20 +- N2 + H O C 1 4- 3 H + + 3C1- (1.8)

 16

T a b l e 4 , P r o p o r t i o n s of monochloramine (Nl12C1) and d i c h l o r a m i n e

(NIIC12) formed a t e q u i l i b r i u m c o n d i t i o n s i n water c h 1 . o r i n a t i o n
w i t h e q u i m o l a r c o n c e n t r a t i o n s of c h l - o r i n c and ammonia as a
f u n c t i o n of t e m p e r a t u r e and pH ( d a t a selected from
Safe D r i n k i n g Water Committee, 1980)O

Proportion Proportion Proportion

at 0 ° C
(%).__I__._
____..I ... 1.0"C
(%) a t _....___ (%) a t 25°C
-___.I.-____
P 11 NH2C1 NHC12 NH2Cl NHClz NH2Cl NWClz

4 0 100 0 1.00 0 100

5 34 66 20 80 13 87

6 77 23 67 33 57 43

7 94 6 81 9 88 12

8 99 1 98 2 97 3

9 100 0 100 0 100 0

a C o n s i d e r a t i o n of k i n e t i c e f f e c t s leads t o c a l c u l a t e d v a l u e s
w i t h lower p r o p o r t i o n s of NHC12.
 17

In acid solutions (pH 4 or less) or in solutions where chlorine con-

centrations far exceed those of ammonia, nitrogen trichloride is formed.
Because nitrogen trichloride is formed from dichloramine [reaction ( 1 6 ) ] ,
the reaction occurs only under conditions in which the dichloramine is
reasonably stable. Thus nitrogen trichloride is the only chloramine at
pH values < 3 . At pH values below 3, monochloramine and dichloramine are
converted to nitrogen trichloride by the following reactions:
4-
3NH2Cl + 2H+ -f NC13 4- 2NH4 , (19)

3NHCl2 + Hf -f 2NC13 + -I-

NHt, . (20)

At chlorine-to-ammonia molar ratios >2, nitrogen trichloride occurs

in diminishing proportions u p to pH values of 7.5. Above pH 7.5, no
nitrogen trichloride is found regardless of the ratio of chlorine to
ammonia (Morris, 1978b).

When chlorine is added to waters containing ammonia, the "breakpoint"

phenomenon becomes significant i n the pH range 6 to 9 (Fig. 2). At
chlorine-to-ammonia molar ratios of 0 up to 1, monochloramine is formed,
and the combined chlorine residual increases to a maximum. At chlorine-
to-ammonia ratios '1, dichloramine is formed. Since it is unstable, it
decomposes as indicated in reaction (18). Thus with the addition of
chlorine, the apparent chlorine residual decreases from a chlorine-to-
anmonia molar ratio of 1 up to %1.65 (the breakpoint) at which point the
ammonia has been converted principally to nitrogen (N2) and some nitrate.
Chlorine that is added after the breakpoint exists as free chlorine [i.e.,
hypochlorous acid and the hypochlorite ion (Pressley et al., 1973; Wei
and Morris, 1974; Morris, 1978b).

Reactions of chloramines. Few chemical studies have been designed

to identify the products resulting from the reaction of chloramines with
organic o r inorganic constituents in water and wastewater, Monochloramine
is a major constituent i n chlorinated wastewaters, and it has been used
as a disinfectant for drinking waters. In aqueous media, the principal
reactions of monochloramine are probably due to hypochlorous acid formed
by hydrolysis and to active chlorine transfer.
18
 19

Monochloramine is less effective as a chlorinating agent than hypo-

chlorous acid by a factor of approximately lo4 (Morris, 1967). Presumably,
many of the reaction products of chlorination of water with free clilorine
will be produced by reaction with combined chlorine residual because of
the hydrolysis of chloramines to hypochlorous acid; however, t h e products
should occur in lower concentrations because of the low equilibrium con-
centrations of the acid. According to Pfargerum et al. (1979), the
hydrolysis of monochloramine,

has a reaction half-time of 10 h. The equilibrium constant is K =

6.7 x at 25OC.

Margerum et al. (1979) indicated that the formation of hydroxylamine

(NH$H),

NH2Cl + 011'- -f NH20H + C1- (22)

at pH 8 and 2 5 ° C h a s a reaction half-time of 350 yr. Therefore, it probably

does not occur in water treatment.

Stevens et al. (1978) determined that trihalomethane (THM) formation

was minimized when chloramines (mostly monochloramine) were used to treat
raw water. Thus during chlorination of water where the ammonia breakpoint
is not achieved, THM production may not be great (Stevens et al., 1978).

Rickabaugh and Kinman (1978) determined that chlorination of Ohio

River water with monochloramine at 10 mg/L, pH 7 to 9 , and 2 5 ° C resulted
in 90.7 to 99.9% less production of THM as compared with 'L'HM production
from chlorination with IO mg per liter of chlorine as hypochlorous and
hypochlorite ion.

Although initially no chlorophenols are formed when low concentratinns

(milligram-per-liter range) of monochloramine and phenol are mixed, they
appear after a reaction time of several days (Burttschell et al., 1959).
This is likely a result of the hydrolysis of NHzC1 and the subsequent
reaction of HOC1 with the phenols.

According t o Margerum et al. (1979), monochloramine is a chlorinating

agent for N-compounds in aqueous solutions. For example, with M
_.
 20

glycine, t h e following r e a c t i o n takes p l a c e :

NH2C1 + H2NCH2COOH -+ H(Cl)NCH2COOH I- N H 3 . (23)

The r a t e c o n s t a n t f o r t h i s r e a c t i o n i s 1 . 5 T, mol-’ s-’ ai pH 5 t o 9 , making

i t o r s i m i l a r r e a c t i o n s p r o b a b l e i n aqueous systems. This report a l s o
c o r r o b o r a t e s t h e o b s e r v a t i o n of E L l i s and Soper (1954) t h a t monochloramine
undergoes c h l o r i n e - e x c h a n g e r e a c t j o n s w i t h p r i m a r y and s e c o n d a r y a l i p h a t i c
amines. S e e a l s o t h e r e s e a r c h of Isaac and M o r r i s (1980) i n t h e f o l l o w i n g
section.

Orgariic.--chlorarni.nes. F r e e chl-orrine a l s o r e a c t s w i t h n i t r o g e n -
c o n t a i n i h g organic. compounds (e.g., amino a c i d s ) t o form o r g a n i c c h l o r -
amines (Cal.vert, 1940; W r i g h t , 1926, 1936; Taras, 1950, 1953; Crane e t a l . ,
194.6; E1li.s and Soper, 1954; Mauger and Soper, 1746; Sandford e t a l . , 1971.;
Edmond and S o p e r , 1 9 4 9 ; I n g o l s e t a l . , 1953; Wajon and M o r r i s , 1980h).
M o r r i s (1967) concluded t h a t t h e r e a c t i o n r a t e s of f r e e c h l o r i n e w i t h
nitrogen-containing coinpounds we-re f a s t e r the h i g h e r t h e b a s i c i t y (nucleo-
p h i l i c i t y ) of t h e compound (Wei.1 and M o r r i s , 1949b). For example, t h e
s e c o n d - o r d e r r e a c t i o n r a t e c o n s t a n t a t 2 5 O C f o r t h e c h l o r i n a t i o n of
methylamine i s 3 . 6 x 1.08 L mol-’ s-’:

A t 25’C and e q u i m o l a r r e a c t a n t c o n c e n t r a t i o n s , t h e r a t e of f o r m a t i o n f o r
N-chloromethylamine i s 70 t i m e s f a s t e r t h a n that- l o r monochloramine.
M o r r i s (1967) a n a l y z e d d a t a from the k i n e t i c s t u d i e s made by Mauger and
Soper (1946) c o n c e r n i n g c h l o r i n a t i o n of amides and concluded t h a t a t e q u i -
molar r e a c t a n t c o n c e n t r a t i o n s t h e f o r m a t i o n of monochloramine w a s much
Faster t h a n t h e f o r m a t i o n of N-chl oramides.

Morris e t a l . (1780) s t a t e t h a t knowledge a b o u t t h e n i t r o g e n -

c o n t a i n i n g o r g a n i c compounds i n n a t u r a l w a t e r s o r a b o u t t h e r e a c t i o n s
of t h e s e compounds w i . t h aqueous c h l o r i n e and t h e p r o p e r t i . e s of t h e pro-
ducts is very limited. This i s u n f o r t u n a t e s i n c e t h e c o n c e n t r a t i o n of
o r g a n i c ami-no-N may g r e a t l y exceed t h a t of ammonia i n s u r f a c e w a t e r s and
some ground waters. Both ammonia c h l o r a m i n e s and o r g a n i c c h l o r a m i n e s are
formed when wastewater effluents a2-e chlorinated. According t o Isaac and
 21

M o r r i s ( 1 9 8 0 ) , t h e r e l a t i v e amounts depend on t h e c o n c e n t r a t i o n r a t i o s
of ammonia t o o r g a n i c amino-N and t h e r e l a t i v e r a t e s of r e a c t i o n . Assuming
2 0 mg/L NH3-N and 2 mg/T, amino-N and r e l a t i v e s p e c i f i c rates o f r e a c t i o n
of 1 t o 8.5 (NH3 t o amino-N), t h e y c a l c u l a t e t h e combined c h l o r i n e would
be 54% NH2C1 and 46% N - c h l o r o o r g a n i c w i t h i n 0 . 3 s a t pH 7 and 25'C. As
t i m e p a s s e s , t r a n s f e r of c h l o r i n e from N H 2 C 1 t o o r g a n i c n i t r o g e n i s f a v o r e d .

Isaac and M o r r i s (1980) s t u d i e d t h e r e a c t i o n of monochloramine w i t h

amino a c i d s ( g l y c i n e , a l a n i n e , and s e r i n e ) , t h e s e c o n d a r y amines ( s a r c o s i n e
and d i m e t h y l a m i n e ) , g l y c l g l y c i n e , and t h e e t h y l e s t e r of g l y c i n e . They
d e m o n s t r a t e d t h a t monochloramine i s an a c t i v e a g e n t f o r t r a n s f e r o f c h l o r i n e
to o t h e r n i t r o g e n atoms. The amino a c i d s are of p a r t i c u l a r i n t e r e s t as
c h l o r i n e r e c e p t o r s b e c a u s e of t h e i r r e l a t i v e abundance i n n a t u r a l waters.
There are two p l a u s i b l e mechanisms f o r C 1
+ t - r a n s f e r from N H Z C 1 t o o r g a n i c
n i t r o g e n - h y d r o l y s i s and d i r e c t t r a n s f e r . I f t h e h y d r o l y s i s mechanism i s
v a l i d , t h e t r a n s f e r r a t e i n t h e p r e s e n c e of e x c e s s n i t r o g e n o u s o r g a n i c
compound s h o u l d b e e q u a l t o t h e h y d r o l y s i s r a t e of monochloramine and i n -
dependent of t h e n a t u r e and c o n c e n t r a t i o n of n i t r o g e n o u s o r g a n i c r e a c t a n t .
Isaac and M o r r i s found t h i s was n o t t h e case when t h e i n i t i a l c o n c e n t r a t i o n
o f n i t r o g e n o u s o r g a n i c compound w a s v a r i e d . I n s t e a d , t h e observed f i r s t -
o r d e r r a t e c o n s t a n t s w e r e p r o p o r t i o n a l t o t h e i n i t i a l c o n c e n t r a t i o n of N-
compound. I n a d d i t i o n , n e a r l y a 20-fold v a r i a t i o n i n t h e r e a c t i o n r a t e
was o b s e r v e d f o r d i f f e r e n t N-compounds. The f i r s t - o r d e r r e a c t i o n r a t e
c o n s t a n t s ranged from 2 x lo'? to 3 x s-l a t 25°C. These values are
g r e a t e r than the chloramine hydrolysis rate, 4 x s-l a t 25°C. They
concluded t h a t N H 2 C l c a n react d i r e c t l y w i t h s u c h compounds t o produce
N-chloroorganics. A t NHZC1 arid o r g a n i c n i t r o g e n c o n c e n t r a t i o n s ( a b o u t
M) i n w a s t e w a t e r e f f l u e n t s and i n r e c e i v i n g waters a t e f f l u c n t tiis-
-_
c h a r g e l o c a t i o n s , d i r e c t r e a c t i o n w i l l o c c u r between N H 2 C 1 arid t h e o r g a n i c
n i t r o g e n compounds t o p r o d u c e N - c h l o r o o r g a n i c s . They concluded t h a t a t
r e a c t a n t c o n c e n t r a t i o n s r e p r e s e n t a t i v e of f r e s h w a t e r ( a b o u t E), both
4-
d i r e c t t r a n s f e r of C 1 t o o r g a n i c n i t r o g e n compounds and NI12Cl h y d r o l y s i s
t o HOC1 w i t h s u b s e q u e n t r e a c t i o n of HOC1 w i t h o r g a n i c n i t r o g e n occur.
The t r a n s f e r of a c t i v e c h l o r i n e from c h l o r a m i n e s t o produce o r g a n i c c M o r -
amines may a f E e c t t h e t o x i c p r o p e r t i e s of t h e c h l o r i n a t e d water ( I s a a c and
M o r r i s , 1980).
 22

2.2.2 Rromamines_..

Hypobromous a c i d reacts w i t h arnnionia and n i t r o g e n - c o n t a i n i n g o r g a n i c s

compounds t o p r o d u c e bromamines and o r g a n i c bromamines. Galal-Gorchrv i ~ n d
M o r r i s (1965) and Johnson and Overby ( 1 9 7 1 ) s t u d i e d t h e f o r m a t i o n of t h e
i n o r g a n i c bromami nes :

H O R r -t- NHBr2 = NKr3 + H20 . (27)

By mixing d i l u t e s o l u t i o n s of bromine w i t h e x c e s s ammonia a t pH 1 9 ,

Galal-Gorchev and M o r r i s (1965) p r e p a r e d s o l u t i o n s of e s s e n t i a l l y p u r e
monobromamine (NEIZBr) as i n d i c a t e d by uv s p e c t r a . With these r e a c t i o n
c o n d i t i o n s , t h e r e d u c t i o n of bromine t o bromide w a s q u i t e r a p i d , a n d a
l a r g e e x c e s s o f ammonia was r e q u i r e d t o s t a b i l . i z e t h e N H 2 B r s o l . u t i o n .
Dibromamine (NHBt-2) s o l u t i o n s as d e t e r m i n e d by IN s p e c t r a were p r e p a r e d
a t pB 5 8 . 2 , b u t t h e r e w a s a c o n s t a n t r e d u c t i o n of bromine t o bromide,
i n d i c a t i n g t h e NHBr2 is unstable. Reaction conditions lending t o t h e
b e s t y i e l d of NHBr2 were pH 5 , 5 t:o 6 . 3 , w i t h a molar r a t i o of ammonia
t o bromine of 20. Tr:ihromamine (NBt-3) formed r e a d i l y a t a c i d i c pH even
i n s o l u t i o n s w i t h a molar r a t i o of ammonia t o bromine >l, i n d i - c a t e d by
uv s p e c t r a . A t pH 4 . 5 , t h e r a t e of r e d u c t i o n of o x i d i z i n g bromine w a s
much s l o w e r , i n d i c a t i n g t h a t NBr3 i s c o n s i d e r a b l y more s t a b l e t h a n N H B r 2 .

In c o n t r a s t w i t h c h l o r a m i n e s , t h e p r o p o r t i o n of bromamine s p e c i e s i n
s o l u t i o n depends on t h e pH and m o l a r r a t i o of ammonia t o bromine ( i s e . ,
t h e d i s t r i b u t i o n i s e q u i l i b r i u m c o n t r o l l e d and r a p i d l y e s t a b l i s h e d ) . In
the c h l o r a m i n e s y s t e m , e q u i l i b r i a are e s t a b l i s h e d s l o w l y , and t h e pro-
p o r t i o n of NH2C1, NHC12, and NCl3 depends on t h e k i n e t i c s of f o r m a t i o n o f
e a c h c h l o r a m i n e speci.c?.s ( L a P o i n t e e t a l . , 1 9 7 5 ) .

Dibromarnine i s t h e predominant bromamine evcn under c o n d i t i o n s w i t h

l a r g e e x c e s s o f ammonia ( e . g . , 100 t o 1 a t pH 7 ) . Monobromamine i s
p r e s e n t o n l y a t h i g h pH a n d / o r h i g h ammonia c o n c e n t r a t i o n s . Tribromamine
can be p r e s e n t up t o pB 9 ( s e e Fig. 3 ) ( L a P o i n t e e t a l . , 1 9 7 5 ) .
 ORNL DWG 01-535

I I I 1 I I I I 7
-2
HOBr om -
-4

0 7--

h,
w
+l

+2

2 3 4 5 6 7 8 9 10

PH
F i g . 3 . Principal species of bromine and bromamine predominating
after 1 to 2 min at various pH and ammonia-to-bromine ratios. Lines
represent equivalent concentrations. Hvpobromous acid separation
from bromine given f o r M bromide (LaPointe et al., 1975).
-
 24

Galal-Gorchev and M o r r i s (1965) and Johnson and Overby (1971) d e t e r -

mined t h a t , q u a l i t a t i v e l y , t h e k i n e t i c s of f o r m a t i o n f o r bromamines w e r e
much f a s t e r t h a n that: f o r t h e ana1.agou.s c h l o r a m i n e s ,

Wajon and M o r r i s (1980a) d e t e r m i n e d t h a t a t pll 7 and 1 ppm NH3-N,

90% o f t h e aqueous bromine i s c o n v e r t e d t o monobromamine i n 0 . 2 s . Di-
bromamine i s formed w i t h i n 1 min a t t h i s pH, whenever t h e m o l a r r a t i o of
n i t r o g e n t o bromine i s <loo, i n d i c a t i n g t h a t t h e dibromamine f o r m a t i o n i s
very rapid. In a d d i t i o n , dibromamine c o n v e r t s v e r y r a p i d l y t o monobrom-
amine when t h e pB changes. Bromine i s , t h u s , a v e r y l a b i l e atom, t r a n s -
f e r r i n g r a p i d l y from one a t t a c h m e n t t o a n o t h e r , w h e t h e r i t i s oxygen, as
i n HORr, o r nitrogen. Johnson and Overby (1971) concluded t h a t t h e d i s -
t r i b u t i o n o f N-bromo compounds i s d e t e r m i n e d p r i n c i p a l l y by e q u i l i b r i u m
c o n s i d e r a t i o n , whereas t h a t of N-chloro compounds i s based o n t h e r e l a c i v e
rates o f formation (Morris, 1967). This conclusion appears v a l i d f o r
r e a c t i o n t i m e s from 1 min t o I h .

Wajon and M o r r i s (1980a) s t u d i e d t h e r e a c t i o n o f aqueous bromine w i t h

ammonia and s e v e r a l amino a c i d s f o r t h e pH r a n g e 9 . 5 t o 1 2 . 7 . According
t o t h e i r d a t a , hypobromous a c i d i s a b o u t 1000 t i m e s more r e a c t i v e toward
ammonia t h a n i s hypobromite i o n . The o v e r a l l rate of f o r m a t i o n o f NB2Br
a t pH 7 i s a b o u t 1 0 t i m e s t h a t o f N H 2 C I . The o b s e r v e d r e a c t i o n r a t e con-
s t a n t a t p H 7 and 2 O o C f o r N H 2 B r f o r m a t i o n was 2 , 9 x lo5 L mol-' s-' and
f o r NHzC1 formation w a s 2 . 1 x lo4 I, mol-' s-l. A t pH 9.5, t h e NH2Br
f o r m a t i o n r e a c t i o n w a s complete w i t h i n 1 . 6 m s . Monobromarnine f o r m a t i o n
w a s second o r d e r , f i r s t o r d e r e a c h w i t h r e s p e c t t o aqueous bromine and
ammonia. Wajon and M o r r i s d e t e r m i n e d t h a t i n c o n t r a s t t o t h e h y p o c h l o r i t e -
ammonia r e a c t i o n f o r which a t a pi1 >IO t h e o b s e r v e d r e a c t i o n r a t e c o n s t a n t
d e c r e a s e d t e n f o l d f o r each u n i t i n c r e a s e i n pH, t h e hypobromite r e a c t i o n
e x h i - b i t e d a l e v e l i n g o f f in r a t e a t pH >11. The d e c r e a s e w i t h t h e
hypochlorite-ammonia r e a c t i o n h a s been a t t r i b u t e d t o a r e a c t i o n mechanism
i n which t h e n o n i o n i c species, HOC1 and NH3, are t h e m a j o r r e a c t a n t s . This
mechanism a l s o a p p e a r s t o be t h e major pathway f o r t h e hypobromite-ammonia
r e a c t i o n a t pH <ll, h u t r e a c t i o n w i t h hypobromite i o n i t s e l f p r o b a b l y ac-
c o u n t s for t h e l e v e l i n g o f f a t pH >11.
 25

The relative kinetics for the formation of bromamines and chloramines

were evaluated by Galal-Gorchev and Morris (1965) based on kinetic data
from Weil and Morris (1949a) and Farkas et al. ( 1 9 4 9 ) , and also experi-
mentally. For equal concentrations of bromide and ammonia nitrogen, the
calculated ratios of formation of monochloramine to hypobromous acid were
750 at pH 9, 110 at pH 8 , 11 at pH 7, and 1.1 at pH 6, Using the follow-
ing concentrations - HOC1 at 2 . 3 x M, ammonium ion at 4.6 x M,
-
and bromide at 4 . 6 x lo-'' -
I

M - Galal-Gorchev and Morris found only mono-

chloramine at pH 8 and above, some bromamine formation at pH 7, and pre-
dominant bromamine formation with rapid l o s s of oxidizing halogen (90%
loss in 7 min) at pH 6 .

The decomposition o f bromamines has been studied principally by

Johnson and coworkers (Johnson and Overby, 1971; Cromer et al., 1978;
Trofe et al., 1979; LaPointe et al., 1975; Inman et al., 1976; Inman and
Johnson, 1978) and more recently by Wajon and Morris (1980a).

Dibromamine is the major bromamine in wastewater disinfected with

bromine. The toxicity of the discharge of a brominated wastewater is
directly related to the stability of dibromamine. Bromamines act as oxi-
dizing agents and are reduced to bromide. Dibromamine is unstable in the
absence of reducing agents and decomposes according to the following
reaction when excess ammonia is present:

3NHBr2 + NH3 -t 2N2 + 6HBr . (28)

Cromer et al. (1978) studied dibromamine decomposition kinetics and deter-

mined that from pH 6 to 8, the formation and decomposition rate of NHBr2
became slower as the pH increased and a l s o as the ammonia-to-bromine molar
ratio increased. Cromer et al. (1978) postulated a possible change in
reaction mechanism to explain the differences at p H 6:

3NHBr2 = 2NBr3 + NH3 ;

NHBr2 4- NRr3 = N2Br4 + H+ + Br- ;

N2Br4 + 2H20 -p N2 + 2 k + 2Br- + 2 H O B r ;

with
 26

-d [NHBr2] [NHBr2]
= =
dt a
~

[NH3]

This reaction mechanism accounts for the observation that mixture:; o f

N W r 2 and NRr3 are most unstable when equivalent amounts of each are
present. Cromer et al. (1978) postulated a second decomposition pathway
to explain the slower rate at pH 7 and 8:

NHBr2 3-NHHr2 -t
kb N2HBr3 + H+ + Br- (33)

N2HBr3 + H20 -f
+
N2 + 2Br- -I- 2H + HOBr ; (34)

with

[NHBr2]2*
v = ka + kb [NHBr2I2 . (35)
[NH3]

Cromer et al. (1978) concluded that the dibrornamine-tribromamine path-

way was the pre€erred decomposition pathway. This mechanism also explains
the slower decomposition rates at higher pH and ammonia-to-bromine ratios
where there is less NBr3. Because of the second-order and higher (2.5)
dependence on dibromamine concentration, the rate of decomposition of
dibromamine becomes quite s l o w at high dilution, high pH, and high ammonia
concentration. They determined the half-life for NHBr2 decomposition at
pH 8 with a 100-fold excess of ammonia and 1 mg/L bromine at 2 O o C was ~3
days.

Wajon and Morris (1980) concluded that dibromamine is considerably

less stable than monobrornamine. At pH 8 and 25'C, the half-life of 5 mg/L
monobromamine is 19 h ( k l = 1 x s-' From Galal-Corchev and Morris,
1965) but the half-life of NHBrz is only 30 min (k2 = 17.5 L mol-' s--'
according to Johnson and Overby, 1971).

Inman et al. (1976) determined that tribromamine decomposes in acid

solutions according to the reaction
-I- -
2NBr3 -+ 3H20 -+ N2 C 3W -t- 3Br t- 3 H O H r ; (36)

and in basic solutions, according to the reaction

 27

2NBr3 + 30H- -+ N2 + 3Br- + 3HOBr . (37)

They determined that tribromamine formed in 5 s under all conditions they

studied. Decomposition of NBr3 was approximately second order. The rate
of NBr3 decomposition increases with increasing pW. They postulated that
-
NBr3 is in equilibrium with NH3r2, NBr2 , HOBr, and OH- and that the de-
composition of NBr3 occurs by a rate-determining step in which NBr3 reacts
-
with NBr2 . The pH dependence o f the reaction rates are accounted for by
.-
postulating hydroxide attack by either NBr3 or NHBrZ to form NBr2 . De-
composition rates are a l s o dependent upon the bromide concentration. At
pH 7 and 8 with low initial bromide and constant ionic strength, the rate
equation for NRr3 decomposition is

where

k
a
2, 1.18 x lo4 L mol-' s-' at 2 S o C .
Galal-Gorchev postulated that tribromamine decomposes directly through
dibromamine. LaPointe et al. (1975) state that this would explain the
stabilizing effect of low ammonia-to-bromine ratios on NBr3 (i.e., because
the entire bromamine system exists in a state of equilibrium, l o w ammonia-
to-bromine ratio shifts the equilibrium towards NBr3). Similarly, high
ammonia concentration in the region where monobromamine is the principal
species will shift the equilibrium towards monobromamine (away from di-
bromamine) and reduce the likelihood of nionobromamine hydrolysis to ammonia
and free bromine. In addition, in the case of NBr3, the probability of
formation is increased with a large excess of bromine. LaPointe et al.
(1975) state decomposition reactions for the entire bromamine system
through dibromamine as governed by equilibria cannot be proven with the
sparse data currently available, but the idea should not be dismissed.

Organic bromamines. Similar to the formation of organic chloramines,

organic bromamines are formed by the reaction of HOBr with nitrogen-
containing organic compounds (e.g., amino acids).
 28

Wajon and M o r r i s (1980a) d e t e r m i n e d t h a t t h e f o r m a t i o n of N-

bromoglycine i s more r a p i d t h a n t h e forrnat.ion of monohromamine. Observed
r e a c t i o n r a t e c o n s t a n t s f o r t h e f o r m a t i o n a t pN 7 and 20°C of N-bromo-
dimethylamine, Ai -bromoglycine, and N-bromoglutainate were 16 x lo4, 4 . 6 x lo5,
and 3 x l.05 L molv1 s-l, r e s p e c t i v e l y . Comparable r e a c t i o n r a t e constants
f o r t h e format:i.cm of 71-chlorodimethylamine and N-chlorogl.ycine w e r e 4 . 3 x lo4
and 1 , 7 x lo5 I, m01.I~ s - l , r e s p e c t i v e l y .

Wajon and M o r r i s (1980a) c o n c l u d e t h a t g l y c i n e and g l u t a m a t e reacC

2 t o 3 times f a s t e r t h a n ammonia w i t h aqueous bromine. Dimethylamine re-
a c t s 1 0 t i m e s as f a s t . O t h e r more b a s i c n i t r o g e n e o u s o r g a n i c compounds
may a l s o r e a c t f a s t e r t h a n ammonia w i t h aqueous bromine. I f t r a n s f e r re-
a c t i o n s of t h e t y p e NH2X + RNH2 equal NH3 +- RNHX a r e r a p i d , t h e d i s t r i b u t i o n
of a c t i v e bromine i n c o o l i n g water b r o m i n a t i o n w i l l be d e t e r m i n e d by t h e
p o s i t i o n o f equilihri-urn. With c h l o r i n e , t h e e q u i l i b r i a l i e f a r on t h e
s i d e of t h e o r g a n i c d e r i v a t i v e s . T f t h e same i s t r u e f o r bromine, most
r e s i d u a l bromine w i l l b e i n t h e form of N-bromoorganic compounds.

'The decomposition of bromamfnes and IT-bromoamino a c i d s i s q u i t e

rapid. A t 25'C t h e h a l f - l i f e of N-bromoglycine a t pH 8.4 h a s been found
t o be 100 min and t h a t of N-bromoglutamate, a b o u t 1.0 min a t pW 9.5.

2 2.3
e Bromochloramines

'The d e c o m p o s i t i o n of monochloramine i n the p r e s e n c e of bromide w a s

s t u d i e d by T r o f e e t al. ( 1 9 7 9 ) . Sugam and Helz ( 1 9 7 7 ) had p r e d i c t e d t h a t
monochloramine c o u l d oxidize. bromide, as e x p r e s s e d by

NH2Cl + Br- -+ N H z B r 3- C l - , (39)

b u t the r e a c t i o n was e x p e c t e d t o b e slow. However, T r o f e e t a l . (1979)

concluded that: t h e d e c o m p o s i t i o n of N H Z C 1 i n t h e p r e s e n c e of bromide i n
saline waters proceeded a c c o r d i n g t o t h e fol.lowing o v e r a l l r e a c t i o n w i t h
t h e f o r m a t i o n of a mixed halamine:

2NH2Cl + Br'- + N H B r C l 3- NH3 f Cl-

where

k = 2,8 x L2 m o l e 2 s-l a t 2 5 O C . (40)

 29

They postulated NHBrCl because of the formation of a peak at 218 nm in

the uv spectra of the reaction products. Such a peak did not agree with
known spectra for bromamines and chloramines. Haag (1980) conclusively
proved the formation and existence of N-bromo-N-chloramines by isolating
and characterizing N-bromo-N-chloromethylamine.

Trofe et al. (1979) concluded that the half-life for monochloramine

at 1 mg/L chlorine in estuarine or marine waters will range from 2.5 to
60 h at salinity ranges from 5 to 35 parts-per-thousand (ppt) and pH from
7 . 5 to 8.0. The major chemical parameters influencing the rapidity of the
decomposition reaction are salinity and pH.

Johnson and coworkers (Johnson, 1977; Inman and Johnson, 1978, 1979)
first pointed out the competition between NHZC1 formation and bromide oxi-
dation when chlorine is added to seawater:

HOCl + NH3 -+kl NH2C1 + H20, kl Q 2.8 x 1.06 L mol-’ S-’ at 25°C: , (41)
k2
HOCl + Br- --+ HOBr + Cl-, k2 Q 3.8 x lo3 L mol-’ s-l a t 2 5 O C . (42)

Haag (1980) stated that the two reaction rates are highly pH depe.ndent
and will be equal at seawater pH 8.1 when the ammonia concentration is
60 ug/L. Haag concluded that bromide oxidation will predominate in most
seawater, with the subsequent generation of bromamines. However, in sea-
water of high ammonia concentration or estuarine waters of lower bromide
and higher ammonia concentrations, the rates f o r both reactions can be
nearly equal. In such cases, a mixture of halamines ranging from mono-
chloramine to bromochloramines to tribromamine would be expected, as
indicated by

NH2C1 + HOBr -f NHBrCl + H20 , (43)

NHBrCl + HOBr -f NBr2C1 + H20 . (441

Haag demonstrated that bromochloramines can be formed under environmental

conditions by these reactions.
 30

C o u r t o t and Peron (1979) e x p e r i m e n t a l l y found N H 2 C 1 , N H 2 B r , and

N H B r 2 t o b e t h e predominant s p e c i e s i n c h l o r i n a t e d seawater when t h e
chlorine-to-ammonia molar r a t i o i s (1.5. If t h e r a t i o i s > 1 . 5 , N B r 3 ,
H O B r , and O B r - were predominant. They d i d n o t l o o k f o r mixed h a l a m i n e s
b e c a u s e t h e y have o n l y r e c e n t l y been r e p o r t e d .

Haag (1980) s t u d i e d t h e d e c o m p o s i t i o n k i n e t i c s o f t h e mixed halamine

C H 3 N B r C 1 and d e t e r m i n e d i t s d e c o m p o s i t i o n r a t e w a s s i m i l a r t o t h a t of
C H 3 N B r 2 and C H 3 N C l 2 a t pIt 8 . 2 and 25°C ( t Q 170 h ) . However, CH3NBrC1
1I 2
decomposes much f a s t e r a t pH 9.7 (t % 1 3 h) o r under l a b o r a t o r y l i g h t
1/2
a t pH 8 . 2 ( t % 40 h ) t h a n d o e s CH3NHC1 under t h e s a m e c o n d i t i o n s (pH 8 . 2 ,
1/2
Q69 d a y s ; pH 9 . 7 , ~ 1 1 0h ; pIi 8 . 2 w i t h l i g h t , 2 7 d a y s ) . Hr?. concluded t h a t
broniochloramines s h o u l d be l e s s p e r s i s t e n t t h a n c h l o r a m i n e s i n t h e e n v i r o n -
ment. .Johnson (1977) i n d i c a L e d t h a t p u r e s o l u t i o n s o f monochloramine a r e
s t a b l e f o r months a t pH 8.

2.2.4 Todamines

Iodamines a r e u n s t a b l e and do n o t f o r m t o a s i g n i f i c a n t e x t e n t i n
aqueous s o l u t i o n s ( S a f e D r i n k i n g Water Committee, 1.980).

2.3 C h l o r i n e Jjemand

Hypochlorous a c i d i s a s t r o n g o x i d a n t a n d , c o n s e q u e n t l y , r e a c t s w i t h
many c o n s t i t u e n t s i n water, When c h l o r i n e i s added t o n a t u r a l water o r
wastewater, t h e c o n c e n t r a t i o n of f r e e a n d / o r combined o x i d a n t i s o b s e r v e d
t o decrease with t i m e . T y p i c a l l y , t h e r a t e of d e c r e a s e i s i n i t i a l l y r a p i d
and t h e n becomes s l o w e r . The d i f f e r e n c e between c h l o r i n e dosage a p p l i e d
t o t h e w a t e r and t h e measured a v a i l a b l e c h l o r i n e i s c a l l e d t h e c h l o r i n e
demand of t h e w a t e r . The c h l o r i n e demand i s p r i n c i p a l l y due t o i n o r g a n i c
o x i d a t i o n r e a c t i o n s and r e a c t i o n s w i t h o r g a n i c c o n s t i t u e n t s (Table 1 ) .

2.3.1 I n o r g .a. n i c. o x i d a t i o n r e a c t i o n s
-

i'he p r i n c i p a l i n o r g a n i c c o n s t i t u e n t s of n a t u r a l w a t e r s and waste-

w a t e r s t h a t r e d u c e free a v a i l a b l e c h l o r i n e ( o x i d a n t ) are t h e f o l l o w i n g :
ammonia, bromide, i r o n ( I 1 ) , m a n g a n e s e ( I I ) , n i t r i t e , s u l f i d e , and s u l f i t e
( M o r r i s , 1978b). The complex r e a c t i o n s o f chi-orine w i t h ammonia and
bromide have been d i s c u s s e d above.
 31

Oxidation of iron(II)-. Aqueous chlorine rapidly and stoichiometri-

cally oxidizes iron(I1). The reaction rate,

2Fe2+ + HOCl + 5H20 -f 2Fe(OH) 4- 5

H
' + Cl- (45)

probably increases with pH (Morris, 1978b).

Oxidation of manganese(l1). possible reactions occur with the

oxidation to manganese(1V) predominating with excess chlorine:

2p.In2+ + HOC1 4- 3H20 -+ ZMnO(0H) + 5Hf 4- C1.- ,

Mn2+ + H O C l f 2Hz0 -f MnO(OH)2 + 3H' + C l - .

The reaction rate increases with increasing pH and is effective for

MnO(OH)2 precipitation above pH 7.5. Manganese(1V) is the most common
interfering material in chlorine residual measurement (Morris, 1978b).

Oxidation of nitrite. Nitrite oxidation is stoichiometric and rapid

at neutral pH values, but slow above pH 9 (Morris, 1978b):

NO^ + HOCL NO^- + ci- .

I

+ H+ 4- (48)

Oxidation of s u l f i d e . The oxidation of sulfide constituents by

chlorine is generally considered to occur by the following reactions:

HS- I- HOC1 + S f H20 + CI-

-
HS- f 4HOCl -+ SOL, + 5H+ + 4C1- .
The first reaction is rapid and complete. With excess chlorine, sulfide
-
is oxidized to sulfate (Sob-). The mechanism is not known. Chlorine
demand because of sulfide is nonstoichiometric, and time, pH, and concen-
tration dependent (Morris, 1 9 7 8 b ) .

Oxidation-of sulfite. Sulfite may be used as a dechlorinating agent,

but may also be found in wastes from treatment of wood-pulp and paper.
The reaction of sulfite with aqueous chlorine is rapid and stoichiometric
(Morris, 1.978b) :
 32

When used f o r d e c h l o r i n a t i o n , i t i s g e n e r a l l y added a s S 0 2 , which r e a c t s

a c c o r d i n g t o t h e f o l l o w i n g r e a c t i o n ( M o r r i s , 1978b):

2.3.2 Decomposition r e a c t i o n s

There a r e two major pathways f o r t h e d e c o m p o s i t i o n o f hypohalous

a c i d s o r h y p o h a l i t e i o n , namely d i s p r o p o r t i o n a t i o n (53) o r d e c o m p o s i t i o n
(54);

-
3HOX -f 3H+ +- 2X- +- X 0 3 (or 30X- -+ 2X- f XO3-) , (53)

2HOX -+ 2H+ + 2X- f 0 2 ( o r 20X- --)- 2X- + 02) . (54)

The pathway and r a t e of d e c o m p o s i t i o n a r e d e t e r m i n e d by pH, c o n c e n t r a t i o n ,

t e m p e r a t u r e , i o n i c s t r e n g t h , and l i g h t (Downs and Adams, 1 9 7 3 ) . The main
r e a c t i o n i n t h e d e c o m p o s i t i o n of h y p o c h l o r i t e i o n i s t h e one t o c h l o r a t e ,
w i t h o n l y a small f r a c t i o n g o i n g t o oxygen ( L i s t e r , 1956a).

~ D i s p r o p o r t i o n a t i o n_-. A t b a s i c pIi v a l u e s , t h e m a j o r d e c o m p o s i t i o n path-

way f o r h y p o h a l i t e i o n s i s d i s p r o p o r t i o n a t i o n :

-
30X- -+ 3X- -I-X 0 3 . (55 1

The e q u i l i b r i u m c o n s t a n t s a r e v e r y f a v o r a b l e w i t h t h e r e a c t i o n r a t e i n -
c r e a s i n g i n t h e sequence OC1- < OBr- < 01-. For OC1-, K n, 3 x 1026,and
t h e r e a c t i o n r a t e i s s l o w a t 2OoC, becoming r a p i d above 7 5 ° C . F o r OBr-,
K n, 8 x l o l l t , and t h e r e a c t i o n r a t e is m o d e r a t e l y f a s t a t 2 0 ° C . F o r OT-,
K n, 5 x 1 0 2 3 , a n d t h e r e a c t i o n r a t e i s f a s t e v e n a t 20°C (Downs and Adanis,
1973).

The d i s p r o p o r t i o n a t i o n of OC1- i s a second-order r e a c t i o n wi.th t h e

f o l l o w i n g mechanism:
 33

-
20c1- + + c1- ,
c102

oc1- + cloy1 -+ c103- + c1-

I

The f i r s t s t e p i s s l o w , and t h e second s t e p i s r e l a t i v e l y f a s t ( L i s t e r ,

1956a). T h e r e a c t i o n i s n o t c a t a l y z e d by manganese, i r o n , c o b a l t , n i c k e l ,
o r c o p p e r o x i d e s ( L i s t e r , 1956b). The h a l i t e (XOz-) i o n i s a l s o an i n t e r -
m e d i a t e i n t h e d i s p r o p o r t i o n a t i o n of OBr- and O r - , which is a u t o c a t a l y z e d
by t h e h a l i d e (X-) i o n (Downs and Adams, 1 9 7 3 ) . The e f f e c t o f c h l o r i d e
i o n on t h e d i s p r o p o r t i o n a t i o n of OC1- i s u n r e s o l v e d . Lewin and Avrahami
(1955) r e p o r t e d t h a t t h e d i s p r o p o r t i o n a t i o n of O C l - a l o n e w a s a c c e l e r a t e d
by t h e a d d i t i o n of c h l o r i d e , whereas Lister (1956b) o b s e r v e d no c a t a l y t i c
e f f e c t s due t o c h l o r i d e .

Hypohalous a c i d s decompose more r a p i d l y t h a n t h e h y p o h a l i t e i o n and

are more p r o n e t o y i e l d oxygen e s p e c i a l l y when s t i m u l a t e d p h o t o c h e m i c a l l y
o r i n t h e p r e s e n c e of c a t a l y t i c metal i o n s . Wypoidous a c i d decomposes
e x c l u s i v e l y by t h e pathway forming oxygen (Downs and Adams, 1 9 7 3 ) . In
a c i d s o l u t i o n s , a p a r a l l e l r e a c t i o n t o p r o d u c e C102 competes w i t h t h e f i n a l
- -
o x i d a t i o n of C l O z t o c103 :

- -
Increasing C102 concentration favors C102 over C l O 3 (Hall et al.,
1981).

According t o M o r r i s (1978b), t h e d i s p r o p o r t i o n a t i o n r e a c t i o n producicig

ClO3
- i s s t r o n g l y i n f l u e n c e d by pH. The maximum r a t e o c c u r s 'bpH 6.7 and
d e c r e a s e s r a p i d l y i n b o t h a c i d and b a s i c s o l u t i o n s . S o l u t i o n s of HOC1 arc
r e l a t i v e l y s t a b l e a t pH 4 . 5 ; O C l - s o l u t i o n s a r e s t a b l e a t p H 1 3 .

Because t h e d i s p r o p o r t i o n a t i o n r e a c t i o n r a t e i s h i g h l y dependent on
r e a c t a n t c o n c e n t r a t i o n s , i t may b e t h e c a u s e of d e t e r i o r a t i o n of s t o c k
-
hypochlorite solutions. However, d i s p r o p o r t i o n a t i o n t o C 1 0 3 is probably
not significant at the milligram-per-liter levels of c h l o r i n e u s e d f o r
water t r e a t m e n t ( M o r r i s , 1 9 7 8 b ) .
 M and
I n t h e pH r a n g e 7 t o 1 0 w i t h e q u a l c o n c e n t r a t i o n s 0.02 t o 0 . 0 5 -
t e m p e r a t u r e s , hypobromite s o l u t i o n s d i s p r o p o r t i o n a t e t o bromate a t a much
h i g h e r r a t e t h a n hypochl.orite s o l u t i o n s . C o n s e q u e n t l y , b e c a u s e b o t h OC1-
and O B r - d i s p r o p o r t i o n a t e by p a s s i n g t h r o u g h t h e s l o w r a t e - d e t e r m i n i n g
h a l i t e s t e p , i t i s a p p a r e n t t h a t HOBr i s much more r e a c t i v e t h a n HOC1 i n
t h e pH r a n g e 7 t o 1 0 (Lewin and Avrahami, 1 9 5 5 ) . The d i s p r o p o r t i o n a t i o n
of hypobromite t o broinate f o l l o w s second-order k i n e t i c s e The r a t e con-
s t a n t f o r O B r - d i s p r o p o r t i o n a t i o n i n c r e a s e s s l i g h t l y w i t h i n c r e a s i n g HOBr-
ORr- o r bromide i o n c o n c e n t r a t i o n , d e c r e a s e s s t r o n g l y w i t h i n c r e a s i n g pH,
and i s i n d e p e n d e n t of c h l o r i d e c o n c e n t r a t i o n up t o 0 . 5 -
M (Lewin and Avrahami,
1955; Engel e t a l . , 1 9 5 4 ) .

Macalady e t a l . (1977) d e t e r m i n e d t h a t s u n l i g h t induced t h e f o r m a t i o n

of bromate i n seawater a t 40°C t h a t had been c h l o r i n a t e d t o 4.2 t o 4 . 9
mg/L c h l o r i n e dosage. The r a t e and e x t e n t of bromate f o r m a t i o n depended
on t h e s u n l i g h t i n t e n s i t y . They o b s e r v e d no bromate f o r m a t i o n i n t h e d a r k .
They concluded t h a t t h e f a c t t h a t t h e y o b s e r v e d no bromate f o r m a t i o n i n t h e
a b s e n c e o.f l i g h t was n o t a t v a r i a n c e w i t h Lewin and Avrahami (1955)
because t h e s o l u t i o n s Macalady and coworkers used were 1000 t i m e s more
dilute. C a l c u l a t i o n s u s i n g r a t e c o n s t a n t s from Lewin and Avrahami i n d i -
c a t e d c o n v e r s i o n t o bromate of ~ 1 a% f t e r 24 h. Wong (1980) a l s o o b s e r v e d
t h a t s u n l i g h t i n d u c e s t h e d e c o m p o s i t i o n of f r e e o x i d a n t ( c h l o r i n e d o s e of
5 mg/T,) i n seawater t o bromate. H e p o s t u l a t e d t h e f o r m a t i o n of an unknown
o x i d a n t species t o a c c o u n t f o r d i f E e r e n c e s bet.ween t i t r a t i o n s a t pH 4.0
and a t pH 1 . 4 . It i s n o t c l e a r w h e t h e r t h i s i s an a r t i f a c t . Bostgaard-
J e n s e n e t a l . (1977) concluded t h a t s u n l i g h t a c c e l e r a t e d t h e decay of
o x i d a n t r e s i d u a l i n a c h l o r i n a t e d m a r i n e c o o l i n g water s y s t e m (pR 8 . 0 and
20 t o 28OC).

Lewin and Avrahami (1955) s t u d i e d t h e o x i d a t i o n of bromide by hypo-

chlorite (see reaction 5). They d e t e r m i n e d t h a t i n t h e pH r a n g e 7 t o 1 0 ,
m i x t u r e s of OC1- and O H r - w e r e u n s t a b l e , and c h l o r a t e and bromate were
-
formed. The r a t e of d e c o m p o s i t i o n of OC1- t o C103 w a s i n c r e a s e d approxi-
m a t e l y t h r e e o r d e r s of magnitude i n t h e p r e s e n c e of bromide.

Haag (1981) d e t e r m i n e d t h a t b o t h bromate and c h l o r a t e a r e p r o d u c t s

of t h e d e c o m p o s i t i o n of f r e e o x i d a n t s i n seawater f o r molar r a t i o s o f >I
 35

for applied chlorine to bromide. Using initial chlorine concentrations

of 200 and 320 mg/L as C12, he determined that bromate and chlorate are
essentially the only products of hypohalite decomposition in the dark
(i.e., no detectable evolution of oxygen). The solutions containing
mixtures of hypobromite and hypochlorite disproportionate to f o r m halates
much faster than separate solutions of pure hypohalites. No chlorate was
formed when the chlorine dosage was less than the equivalent bromide in
the seawater; however, bromate was formed. Haag concluded this was n o t at
variance with Carpenter and Macalady (1978) or Wong and Davidson (3.977)
who had detected no bromate in seawater after decomposition of oxidant
residual in the dark because of the longer times and much higher concen-
trations that he used. Haag determined that no rate enhancement @xi-sts f o r
mixed hypohalite systems exposed to sunlight, although halate formation is
much more rapid than in the dark. Haag (1981) concluded that rate enhance-
ment in the formation of chlorate and bromate could occur in the chlori-
nation of cooling waters from the upper reaches of an estuary where approxi-
mately a 1:l mixture of HOC1 and HOBr might exist after satisfaction of
demand reactions.

Decomposition to oxygen. Hypohalous acid and hypohalite decomposition

t o oxygen is slow in the dark, as indicated by

20x- -> 2x- f 02 - (59)

Lister (1956b) found copper, nickel, and cobalt catalyzed the p r o -

duction of 02. In 1 -
M sodium hypochlorite solution at 5OoC using
moles of metal the rates of oxygen production were: Cu, 7 . 4 mT.,/min;Co,
4.0 mL/min; Ni, 2.0 mL/min. Manganese and iron do not catalyze the
reaction.

In a later study, Lister and Petterson (1962) determined that the

rate of oxygen evolution is second order with respect to hypochlorite.
The rate constant is 1.25 x 1.. s-' at 60°C.

The significance of photochemically accelerated decomposition of

oxidant residuals to oxygen is not known.
 36

2.3.3 Reactions w i t h
-_._I

A l a r g c v a r i e t y of r e a c t i o n s may o c c u r between f r e e a v a i l a b l e
c h l o r i n e (HOC1 OCl-) and t h e complex m i x t u r e s o f o r g a n i c c o n s t i tuents
p r e s e n t i n n a t u r a l waters and wastewaters. The f o l l o w i n g t r e a t m e n t i s
m e r e l y d e s i g n e d t o h i g h l i g h t p o s s i b l e o r g a n i c r e a c t i o n s and i s n o t i n -
tended t o be e x h a u s t i v e .
The t y p e s and c o n c e n t r a t i o n s of o r g a n i c p r o d u c t s of c h l o r i n a t i o n re-
actions are a f u n c t i o n of t h e r e a c t a n t c - o n c e n t r a t i o n s , r e a c t i o n k i n e t i c s ,
pH, t e m p e r a t u r e , and p r e s e n c e of o t h e r h a l i d e s o r ammonia. Some p r o d u c t s
(e.g., t r i h a l o m e t h a n e s ) appear t o be u b i q u i t o u s . The p o s s i b l e r e a c t i o n s
of c h l o r i n e w i t h o r g a n i c c o n s t i t u e n t s i n n a t u r a l w a t e r s and wastewaters
and p r o d u c t s have been e x t e n s i v e l y summarized and reviewed ( J o l l e y , 1.973,
1978; J o l l e y e t al., 197813, 1980; M o r r i s , 1975; Symons e t a l . , 1975;
Di-enzer e t a l . , 1978; P i e r c e , 1978; M o r r i s e t al., 1980; S a f e D r i n k i n g
Water Committee, 1980; Hall e t a l . , 1.98l). Only major r e a c t i o n t y p e s
and s e l e c t e d s p e c i f i c examples w i l l b e reviewed below.

The p o s s i b l e c h e m i c a l r e a c t i o n s of f r e e c h l o r i n e w i t h o r g a n i c con-
s t i t u e n t s i n aqueous s o l u t i o n may b e grouped i n t o s e v e r a l general. t y p e s
( T a b l e 1): (1.) o x i d a t i o n , ( 2 ) a d d i t i o n , and ( 3 ) s u b s t i t u t i o n ( i . e . , the
f o r m a t i o n of b o t h N - c h l o r i n a t e d compounds and C - c h l o r i n a t e d compounds).

IOxidation. O x i d a t i o n may b e t h e predominant t y p e o f r e a c t i o n oc-

c u r r i n g between l l O C l and o r g a n i c c o n s t i t u e n t s i n n a t u r a l waters and waste-
waters ( J o l - l e y , 1 9 7 3 , 1978; Christman et a l . , 1 9 8 0 ) . The c a r b o h y d r a t e s
and c a r b o h y d r a t e - r e l a t e d compounds are examples o f o r g a n i c s which are
s u b j e c t p r i n c i p a l l y t o o x i - d a t i v e r e a c t i o n s ( s e e Crane e t al., 1980).

Addition. Hypochlorous a c i d w i l l r e a c t w i t h o r g a n l c s c o n t a i n i n g
r e a c t i v e d o u b l e bonds t o p r o d u c e c h l o r o h y d r i n p r o d u c t s For exampl-e,
o l e i c a c i d r e a c t s w i t h HOC1 a t pi3 2 t o 10 t o produce 9-chloro-10-hydroxy-
st.earic a c i d ( C a r l s o n and C a p l e , 1 9 7 8 ) .

Substitution. C h l o r i n e may r e a c t with a r o m a t i c compounds and amino

compounds t o replace a hydrogen s u b s t i t u e n t p r o d u c i n g C - c h l o r i n a t e d or
N-chi-orinated compounds. 'The f o r m a t i o n of N - c h l o r o o r g a n i c s h a s been
discussed in some detail elsewhere in this review. The production of
trihalomethanes and reactions with humic substances and aromatic con-
stituents are examples of substitution reactions in which carbon-chlorine
bonds are produced.

Since Rook (1974) and Bellar et al. (1974) reported the presence of
chloroform and other trihalomethanes ( T I M ) in drinking water, THMs have
been shown to be essentially ubiquitous in chlorinated waters including
seawater ( H e l z and Hsu, 1978). Much data are now abailable concerning
THM precursors, THM production, and analysis (Jolley, 1978; Jolley et al.,
1978a,b; Hoehn et al., 1978; Morris and Baum, 1978; Minear and Bird, 1980;
Safe Drinking Water Committee, 1980). Numerous studies indicate that
temperature, season of the year, pH, organic content of the water,
chlorine dose, and chlorine contact time can influence the concentration
levels of trihalomethanes in the chlorinated water. In general, the tri-
halomethane concentration is directly dependent upon the chlorine d o s e ,
the organic content of the water, the contact time, and the temperature.
This conclusion can probably be extrapolated to the nonvolatile chlori-
nated by-products.

Humic materials have been implicated as being THM precursor material.

In addition to THM, nonvolatile chlororganics may be produced by chlori-
nation of humic materials. Research in this area is increasing (see
Jolley, 1978; Jolley et al., 1978b, 1980; G l a z e et al., 1980; Helz et al.,
1978). Space permits citing only selected examples of current research.

Christman et al. (1980) studied the chlorination at pH 12 of aquatic

humic material separated from Black Lake, North Carolina, with the objec-
tives of gaining insight into the types of compounds present in chlori-
nated drinking water as well as structural information about the humic
acid molecule. Three main classes of compounds were detected in the
reaction mixture in which humic acid had a concentration of 420 mg carbon
per liter and chlorine at a chlorine-to-carbon mol ratio of 1.5. These
classes were norichlorinated substituted aromatic constituents, nonchlori-
nated straight-chain acids, and chlorinated straight-chain acids.

Rook (1980) examined the chlorination of humic materials from two

points of view: (1) the influence of functional groups on the reactivity
o f c h l o r i n e and bromine w i t h a r o m a t i c c o n s t i t u e n t s u s i n g a p p r o p r i a t e
model compounds; and ( 2 ) d e g r a d a t i o n pathways f o r humic m a t e r i a l by
e x a m i n a t i o n of t h e r e a c t i o n p r o d u c t s o f r e s o r c i n o l . R e s u l t s from t h e s e
two a p p r o a c h e s w e r e t h e n u s e d t o f o r m u l a t e a proposed pathway f o r t h e
d e g r a d a t i o n of humic a c i d s by c h l o r i n a t i o n . The r e a c t i o n pathways pro-
posed a c c o u n t f o r most of t h e major d e g r a d a t i o n p r o d u c t s found i n re-
a c t i o n m i x t u r e s of c h l o r i n e and humic materials. A f t e r breakpoint
c h l o r i n a t i o n , two classes of c h l o r i n a t e d and brominated by-products are
found i n f i n i s h e d d r i n k i n g water: (1) v o l a t i l e t r i h a l o m e t h a n e s , and
( 2 ) n o n v o l a t i l e h a l o g e n a t e d compounds. Rook s t a t e d t h a t t h e m a j o r i t y
of t h e c h l o r i n a t e d a l i p h a t i c and a r o m a t i c d e g r a d a t i o n by-products formed
on c h l o r i n a t i o n of hum.ic a c i d c o n t a i n i n g waters are o f t h e n o n v o l a t i l e
halogenated c l a s s .

Some a r o m a t i c compounds s u c h as p h e n o l s are r e a d i l y c h l o r i n a t e d i n

aqueous s o l u t i o n by f r e e c h l o r i - n e . Some ni.trogerrous o r g a n i c compounds
a l s o undergo c h l o r i n a t i o n s u b s t i t u t i o n r e a c t i o n s . For example, t h e
p y r i m i d i n e u r a c i l r e a c t s w i t h aqueous HOC1 t o f o r m 5 - c h l o r o u r a c i l
( J o l l e y , 1973).

Wajon and M o r r i s (1980b) have s t u d i e d t h e c h l o r i n a t i o n o f many

n i t r o g e n o u s compounds and found t h e r e a c t i o n p r o d u c t s t o b e q u i t e v a r i e d .
For exampl-e, some amino a c i d s and h e t e r o c y c l i c b a s e s react: r e a d i l y t o
forin N-chloroamino a c i d s and N - c h l o r o h e t e r o c y c l i c compounds which are
d e t e c t a b l e a n a l y t i c a l l y as f r e e a v a i l a b l e c h l o r i n e ; o t h e r amino a c i d s
and h e t e r o c y c l i c b a s e s may react w i t h c h l o r i n e , b u t t h e reaction product:
i s n o t d e t e c t a b l e as a v a i l a b l e c h l o r i n e . T h i s phenomenon h a s c o n s i d e r a b l e
s i g n i f i c a n c e f o r t h e i n t e r p r e t a t i o n o f a n a l y t i c a l r e s u l t s o h t a i n e d on
c h l o r i n a t e d waters c o n t a i n i n g n i t r o g e n o u s o r g a n i c compounds. Presumably,
t h e r e a c t i o n p r o d u c t s n o t d e t e c t a b l e as e i t h e r f r e e o r combined a v a i l a b l e
c h l o r i . n e may i n c l u d e c h l o r o o r g a n i c s and o x i d i z e d o r g a n i c s . Because of
t h e o b s e r v e d d i f f e r e n t b e h a v i o r s of t h e i n d i v i d u a l compounds, no g e n e r a l -
i z a t i o n s a b o u t t h i s group can b e made.
 39

3. ANALYTICAL METHODS FOR OXIDANT SPECIES

IN CHLORINATED WATERS

Chlorine present in aqueous solution as hypochlorous acid and

hypochlorite ion is called "free chlorine" (free residual chlorine).
Although generally of little consequence in waters at near-neutral pH
values, molecular chlorine and nitrogen trichloride are a l s o usually
analyzed as free chlorine. Chlorine present as monochloramine (NHZCl),
dichloramine (NHCl2), and N-chloroorganic compounds in which the chlorine-
containing compound has a lower oxidation potential than free chlorine
or slow reaction rate is called "combined chlorine'' (combined residual
chlorine). These compounds frequently react slower than the free
chlorine species in disinfection processes and chemical reactions in-
volved in analytical determinations. Iodide can accelerate some of the
chemical reactions of combined species in analysis procedures. "Total
chlorine" (total residual chlorine) is the sum of the free and combined
available chlorine.

Bromide and iodide, when present at even trace concentrations, are

oxidized by chlorine to HOBr and HQI and, consequently, will be detected
by the usual analytical methods as free available chlorine. Hypobromous
acid will also react with ammonia to produce bromamines. Thus the terms
free oxidant and combined oxidant: are more appropriate than free chlorine
and combined chlorine when such solutions (e.g., seawater) are the subject
of analysis. However, present analytical methods may not differentiate
between free and combined bromine species.

Analytical results are customarily reported as nominal chlorine mass

units (e.g., as mg/L chlorine). Hall et al. ( 1 9 8 1 ) believe a convenient
and more general. unit -is microequivalent per l i t e r or micronormality (;IN)
particularly when chemical reactions are considered.

The basic questions underlying a l l analytical determinations concern

the meaning of the measurement. Can the measurement be related to the
real world situation? Can cause-effect relationships b e deduced from
observed phenomena associated with the analytical measurement? Can action
be predicated based on such association and analyses?
 40

The d i f f i c u l t y of q u a n t i t a t i v e d e t e r m i n a t i o n of c h l o r i n e - c o n t a i n i n g
s p e c i e s o r o t h e r h a l o g e n o r o x i d a n t s p e c i e s r e s u l t i n g f r o m t h e chi-ori-
n a t i o n of waters i s a f u n c t i o n o f the c h e m i c a l c o m p l e x i t y of t h e water
system. The r e a l meaning of s u c h measurement i s dependent upon t h e i n -
h e r e n t l i m i t a t i o n s of t h e a n a l y t i c a l t e c h n i q u e o r method, t h e water q u a l i t y
( c h e m i c a l c o m p o s i t i o n of t h e s a m p l e ) , t h e s p e c i f i c h i s t o r y of the sample
being analyzed ( i . e . , how and when c o l l e c t e d , method of p r e s e r v a t i o n , and
time-frame o f a n a l y s i s ) , and t h e e x p e r i e n c e , knowledge, and t e c h n i q u e o f
the analyst. C r i t i c a l a n a l y s i s of e x t a n t l i t e r a t u r e must be c o g n i z a n t o f
such f a c t o r s . For example, r e s u l t s from t h e u s e of t h e most a c c u r a t e and
p r e c i s e a n a l y t i c a l method may be r e n d e r e d of no v a l u e by p o o r t e c h n i q u e ,
such as f a u l t y equipment or d e t e r i o r a t e d r e a g e n t s . Conversely, a n
a n a l y t i c a l t e c h n i q u e w i t h i n h e r e n t l y p o o r e r a c c u r a c y and p r e c i s i o n may
y i e l d a c c e p t a b l e d a t a i n t h e hands o f a s k i l l e d , knowledgeable o p e r a t o r ,
o r i f h i g h - q u a l i t y w a t e r i s analyzed. Sorber e t a l . (1977) have s t a t e d
t h a t most p u b l i s h e d p r o c e d u r e s p e r f o r m w e l l i n r e l a t i v e l y c l e a n s y s t e m s
f r e e from i n t e r f e r e n c e s . S o l l o e t al. (1970) examined t h e d a t a r e p o r t e d
by L i s h k a e t a l . (1969),comparing n i n e a n a l y t i c a l methods f o r f r e e and
t o t a l chlorine. From t h e d a t a S o l l o and coworkers concluded t h a t e a c h
method when u s e d p r o p e r l y and a c c o r d i n g t o s p e c i f i e d i n s t r u c t i o n s c a n b e
acceptable. They concluded the f a i l u r e s were due t o p o o r l a b o r a t o r y
p r o c e d u r e and n o t t o p r e s c r i b e d methodology.

Voluminous l i t e r a t u r e e x i s t s c o n c e r n i n g a n a l y s i s of c h l o r i n e - and
o t h e r halogen-containing s p e c i e s i n aqueous s o l u t i o n . This 1i.terature
has been w e l l reviewed (Opresko, 1980; H a l l e t a l . , 1981; Marks, 1972;
I l e l z , 1980; S t a n h r d Methods, 1975; Whit:e, 1972) and many a n a l y t i c a l
inetiiods have b e e n compared w i t h r e s p e c t t o a c c u r a c y and p r e c i s i o n
(Sengupta e t a l . , 1978; Johnson, 1978; L i s k a e t a l . , 1969; S o l l o e t a l . ,
1.970; S o r b e r et a l . , 1 9 7 7 ; Lishka and McFarren, 1973.; Bender, 1978;
N i c o l s o n , 1965; G u t e r and Cooper, 1 9 7 2 ) . T h i s l i t e r a t u r e and s e l e c t e d
p a p e r s c o n c e r n i n g s p e c i f i.c p r o c e d u r e development liave been reviewed w i t h
two p r i n c i p a l o b j e c t i v e s i n mind, namely: (1) d e t e r m i n a t i o n of t h e ac-
c u r a c y and p r e c i s i o n of t h e a n a l y t i c a l method r e l a t i v e t o t o x i c i t y tests;
and (2) d e t e r m i n a t i o n of t h e s e n s i t i v i t y , a c c u r a c y , and r e l i a b i l i t y of
 41

the analytical method relative to analysis of low concentrations of

chlorine or oxidant.

This report only reviews the analytical methods for determining

available chlorine, "Cl'", and other oxidant species formed by chlori-
nation of water (e.g., HOBr). The analysis of both inorganic and organic
reaction products ( e . g . , bromates, trihalomethanes, nonvolatile halo-
organics, etc.) is beyond the scope of this review.

A large number of analytical methods are available for determining

the available chlorine or oxidant in waters. Standard Methods (1975)
lists several methods accepted for use in the control of disinfection of
drinking water and wastewaters. Helz (1980) has grouped the methods into
three major types: colorimetry, potentiometry, and amperometry. However,
this misses the important distinction between measurement of some property
of the free or combined oxidants and the alternative of titrimetric oxi-
dant estimation using some property for equivalence point detection. The
critical point is that, for the direct measurement approach, standards
covering the whole range of analyte concentrations need to be prepared to
verify that the sensing system is performing as expected; whereas, for
titrimetric techniques, only the titrant strength needs to be standardized
against some reference substance.

For this review, the analytical methods have been grouped into the
following categories :
1. Direct property measurement
a. Potentiometry
b. Amperometry
c. Spectrophotometry
2. Colorimetry
3. Chemiluminescence
4.. Titrimetry

3.1 General Analytical Considerations

Several compounds may be present in water or formed on chlorination

of water that are falsely measured as chlorine by most of the analytical
 42

methods. These compounds may t h u s b e i n c o r r e c t l y i n t e r p r e t e d as a v a i l a b l e

c h l o r i n e i n e i t h e r t h e f r e e o r combined c h l o r i n e f r a c t i . o n s . Johnson (1978)
s t a t e d t h a t t h e most common i n t e r f e r e n c e t n f r e e c h l o r i n e measurements i s
manganese(1V) o x i d e formed by c h l o r i n e o x i d a t i o n of s o l u b l e inanganous(I1)
ion. I n g e n e r a l , a l l s t r o n g o x i d a n t s w i l l i n t e r f e r e i n c h l o r i n e measure-
ments. Sengupta e t a l . (1978) p r e s e n t e d a l i s t of p o s s i b l e s t r o n g i n t e r -
-
fering oxidants. Many, s u c h as 0 2 and I O 3 ,will react o n l y s l o w l y under
norrnal a n a l y t i c a l c o n d i t i o n s . O f most i m p o r t a n c e on a n abundance b a s i s
are F e and Mn. C o p p e r ( I 1 ) may b e of i m p o r t a n c e i n power p l a n t s w i t h
c o p p e r l n i c k e l c o n d e n s e r t u b e s and h i g h c o r r o s i o n r a t e s . I n waters h i g h l y
p o l l u t e d by a g r i c u l t u r a l r u n o f f and wastewaters, n i t r i t e and n i t r a t e may
be important. Most i n t e r f e r e n c e s may b e c o n t r o l l e d by compensatory manip-
u l a t i o n of r e a g e n t c o n c e n t r a t i o n s i f t h e a n a l y s t i s aware of t h e i r p r e s e n c e .

Most methods t h a t measure t o t a l a v a i l a b J e c h l o r i n e ( c h l o r i n e produced

o x i d a n t s ) u t i l i z e i o d i d e s a l t s a t some s t a g e of t h e a n a l y s i s b e c a u s e of
t h e following chemical r e a c t i o n :

i n which X r e p r e s e n t s a r e l a t i v e l y l a b i l e h a l o g e n atom. 'The r e a c t i o n g o e s

s p o n t a n e o u s l y t o t h e r i g h t a t r e l a t i v e l y l o w C- c o n c e n t r a t i o n s and n e u t r a l
pH r a n g e ( 6 t o 8 ) w i t h s t r o n g o x i d a n t s s u c h as HOC1, H O B r , and monochlor-
a m i n e (NH2C1). F o r less s t r o n g o x i d a n t s [e.g., d i c h l o r a m i n e (NHC12)], t-he
r e a c t i o n i s enhanced by i n c r e a s i n g t h e 1- c o n c e n t r a t i o n and a c i d i t y
(Sengupta e t a l . , 1978). The i o d i n e (12) produced from r e a c t i o n (60) can
h e measured i n a v a r i e t y of ways and s u c h measurements Form t h e b a s i s f o r
many of t h e a n a l y t i c a l methods d i s c u s s e d i n t h i s c h a p t e r .

Bromine o x i d a n t s p e c i e s t h a t might b e p r e s e n t i n c h l o r i n a t e d f r e s h
o r e s t u a r i n e waters are c a p a b l e o f r e a c t i n g q u a n t i t a t i v e l y w i t h I- t o
- - -
form 112, 1 3 , and I O 3 . The p r o p o r t i o n of 12 t o 1 3 i s c o n t r o l l e d by
t h e c o n c e n t r a t i o n of I-, as i n d i c a t e d i n r e a c t i o n ( 6 1 ) :
 43

Iodate (IO3-) c a n b e c o n v e r t e d t o 12 by i n c r e a s i n g i o d i d e c o n c e n t r a t i o n
and a c i d i t y , as shown i n r e a c t i o n (62) (Sengupta e t al., 1 9 7 8 ) ,

Seawater c o n t a i n s %60 vg/L t o t a l i o d i n e t h a t i s p r e s e n t i n oxygen-

a t e d s u r f a c e waters as I O 3
-. (Sengupta e t a l . , 1978; Wong and B r e w e r ,
1977). I f o x i d a n t a n a l y s i s i s performed u s i n g c o n d i t i o n s p e r m i t t i n g t h e
- .,
d e t e c t i o n of Io3 , t h e n IO3 may c o n t r i b u t e t o a background o x i d a n t l e v e l .
F r e s h w a t e r r i v e r s and l a k e s c o n t a i n on t h e a v e r a g e 2 pg/L e l e m e n t a l i o d i n e .
Thus, s i m i l a r l y t o t h e seawater s i t u a t i o n , i o d i n e may c o n t r i b u t e t o s m a l l
-
background o x i d a n t l e v e l t o t h e e x t e n t i t i s p r e s e n t as 103 . Mixtures
of f r e s h w a t e r and seawater as i n e s t u a r i n e areas p o s s e s s i n t e r m e d i a t e
background o x i d a n t levels i n s u c h a n a l y s e s . I o d a t e w i l l n o t b e detlected
by most of t h e a v a i l a b l e c h l o r i n e ( o x i d a n t ) a n a l y s e s . However, 1 0 3 can
I

b e c o n v e r t e d t o I2 a c c o r d i n g to r e a c t i o n ( 6 2 ) . The r e a c t i o n r a t e i s
d i r e c t l y p r o p o r t i o n a l t o I- and H
+ c o n c e n t r a t i o n (Sengupta e t a l . , 1 9 7 8 ) .

The o x i d a t i o n of 1- by oxygen [ r e a c t i o n (6311 d u r i n g t h e c o u r s e of

t h e a n a l y s i s o r d u r i n g s h e l f s t o r a g e of t h e r e a g e n t s o l u t i o n i s a poten-
t i a l l y s e r i o u s i n t e r f e r e n c e w i t h low-level oxidant analyses:

41- 1- 02 3- 4H+ = 212 f 21120 . (63)

T h i s r e a c t i o n i s s l o w a t n e u t r a l pH b u t i s a c c e l e r a t e d by i n c r e a s i n g
a c i d i t y ( d e c r e a s i n g pH), by l i g h t , and by traces of C u ( I 1 ) and n i t r o g e n
oxides. Sengupta et al. (1978) i n d i c a t e d t h i s may be t h e s o u r c e of re-
p o r t e d background o x i d a n t levels >lo ug/Z as c h l o r i n e i n u n c h l o r i n a t e d
water. They recommended u s i n g K I r e a g e n t p r e p a r e d f r e s h e a c h day.
Ridgon (1978) used K I i n 0.025 NaOH which e l i m i n a t e d backgroiind
o x i d a n t l e v e l s and t h e need f o r d a i l y r e a g e n t p r e p a r a t i o n .

Sengupta e t a l . (1978) t h o r o u g h l y d i s c u s s p o t e n t i a l n e g a t i v e e r r o r s .
The most f r e q u e n t l y c i t e d e r r o r i s v o l a t i l i z a t i o n of 12 o r o t h e r h a l o g e n
species d u r i n g t h e c o u r s e of a n a l y s i s . ‘rhe magnitude of t h i s e r r o r i s
Limited t o o n l y a few p e r c e n t i f t h e a n a l y s i s i s accomplished w i t h i n a
 44

few m i n u t e s a f t e r K 1 a d d i t i o n . However, t h i s i s a s i g n i f i c a n t problem

f o r aniperometric t i t r a t i o n of Low c o n c e n t r a t i o n s of c h l o r i n e , They i n d i -
c a t e a d s o r p t i o n of I2 on g l a s s w a r e i s u s u a l l y o n l y a minor e r r o r , b u t
a d s o r p t i o n on suspended i n o r g a n i c o r o r g a n i c p a r t i c l e s may b e more s i g -
nificant. An i m p o r t a n t l o s s of 12 d u r i n g Lhe a n a l y s i s of h i g h l y p o l l u t e d
water ( e . g . , sewage t r e a t m e n t p l a n t e f f l u e n t s ) i s t h e r e a c t i o n of 12 w i t h
o r g a n i c matter. However, t h e most s e r i o u s p o t e n t i a l n e g a t i v e e r r o r may
b e t h e formation of o x i d a t i v e c h l o r i n e by-products t h a t may b e u n d e t e c t e d
d u r i n g t h e t i m e p e r i o d of t h e a n a l y s i s ( C a r p e n t e r and Macalady, 1 9 7 8 ;
I
Macalady et: a l . , 1977; C a r p e n t e r e t a l . , 1 9 7 7 ) .

A s e r i o u s p o t e n t i a l problem c r e a t e d by t h e u s e of i o d i d e i s t h a t
many o x i d a n t s w i l l o x i d i z e iodi.de t o i o d i n e . T h e r e f o r e , a n a l y t i c a l methods
u s i n g i o d i d e are n o t s p e c i f i c ; f o r example, more s u b s t a n c e s will i n t e r f e r e
w i t h t o t a l c h l o r i n e d e t e r m i n a t i o n s t h a n w i t h f r e e c h l o r i n e measurements.

Another p o t e n t i a l a n a l y t i c a l e r r o r i s t h e change i n c h e m i c a l s p e c i -
a t i o n of t h e o x i d a n t due t o changing t h e pH of t h e water s a m p l e p r i o r t o
f i x a t i o n of t h e species d u r i n g t h e c h e m i c a l a n a l y s i s . Most a n a l y t i c a l
methods f o r s p e c i f i c c h e m i c a l s p e c i e s t a k e t h i s f a c t o r i n t o c o n s i d e r a t i o n .

Water samples c o l l e c t e d f o r a v a i l a b l e c h l o r i n e o r o x i d a n t a n a l y s i s
must be a n a l y z e d soon a f t e r c o l l e c t i o n b e c a u s e of t h e i n s t a b i l i t y of
a v a t l a b l e o x i d a n t s p e c i e s and d e g r a d a t i o n r e a c t i o n s . The p r a c t i c e of
"f:i.xing" t h e a v a i l a b l e o x i d a n t by a d d i n g a known amount of r e d u c t a n t i.n
s t o i c h i o m e t r i c e x c e s s t h e n back t i t r a t i . n g w i t h a s t a n d a r d o x i d a n t can b e
a useful technique. Such t e c h n i q u e s r e q u i r e c o n s i d e r a b l e p r e c i s i o n and
care, knowledge of t h e s t o r a g e s t a b i l i t y of t h e added r e d u c t a n t , and
r e a s o n a b l y a c c u r a t e knowledge of t h e o x i d a n t c o n c e n t r a t i o n s o t h a t the
q u a n t i t y of added r e d u c t a n t does n o t g r e a . t l y exceed t h e o x i d a n t .

3 , l,1. D e f i n i t i . o n of Terms

A s a p p l i e d t o methods of c h e m i c a l a n a l y s i s , p r e c i s i o n refers t o t h e
r e p r o d u c i b i l i t y of a method when i t i s r e p e a t e d on a sample under con-
t r o l l e d conditions. P r e c i s i o n can b e e x p r e s s e d as t h e s t a n d a r d d e v i a t i o n
(0) according t o t h e following equation:
 45

where x is the observed value, and ‘ii. is the average observed value in n
observations (Standard Methods, 1975).

Accuracy refers to the agreement between the observed value and the
amount of measured component actually present in the sample. The relative
error expresses the difference between the measured or observed value and
the actual amount, as a percentage of the actual amount ( S t a n h r d Methods,
1975).

The minimum detectable concentration or limit of detection is a

function of the reproducibility of the blank value. If the blank value
were perfectly reproducible, the limit of detection would be determined
by the smallest discrimination obtainable with the instrument or method
being used (Nicolson, 1965). For purposes of this review, the limit of
detection for colorimetric o r spectrophotometric methods is defined as
the concentration of component that gives an absorbance of 0.001 using a
1-cm patlh length (Nicolson, 1965). This may be calculated f r o m molar
absorptivity (E) using the following relations :

A x MhT
C =
EX^ ’

where C is concentration, A is absorbance, MW i s the molecular weight

(e.g., 70 for chlorine), E is the molar absorptivity, and b is the optical
path length.

The minimum limit of detection for amperometric and potentiometric

methods is usually defined as two times the noise level of the measure-
ment. Because this is customarily not reported for such methods, the
limit of detection used is that reported by the investigators.

3.1.2 Sampling

I n analytical chemistry there is an axiom that the result of any

analytical procedure can be no better than the sample on which it: is
 46

performed. The objective of sampling is to collect a representative

sample and to handle i.t in such a way that no significant change in com-
position occurs prior to the analysis. See Stm&z%! Msthods (1975) for
general sampling considerations-

Because of the labile nature of chlorine and oxidant species in

water samples, the samples must be amlyzed expeditiously. Exposure to
sunlight or other strong light or agitation will accelerate the loss of
chlorine. Therefore, chlorine determinations should be started immediately
after sampling thus avoiding extensi~ve light and agitation. Standapd
Methods (1975) recommends to not store samples that are to be analyzed
f o r chlorine, Therefore, samples to be analyzed f o r chlorine must be
either grab samples analyzed immediately after sampling or must be con-
tinuously analyzed by on-line monitors, However, several analytical pro-
cedures use addition of excess reductant (e.R . , phenvlarsine oxide) to
reduce the chlorine and other oxidant species immediately upon the
collection of the sample, thus permitting analysis by "back titration"
later at the laboratory. These methods presumably are as accurate as
the "forward" methods; however, judging the amount of reductant to add
may require taking more samples i n order t o bracket the stoichiometric
amount of reductant required. See Standard Mgt-hods (1975) f o r specific
details regarding back titration procedures. Deci-sions regarding sampling
methodology must be made on a site-specific basis taking into consideration
the analytical methodology t o be used.

3,2 Potentiometry

Potentiometry invol.ves the measurement of the spontaneous electrical

potential generated between two dissimilar electrodes in a solution. One
electrode is chosen to be insensiti-vet o the solution composition ( t h e
reference electrode), and the other electrode ideal-ly responds exc1usivel.y
t o the concentration of the analyte (Willard et al., 1965). F o r free
oxidants produced by chlorination, the sensing electrode is commonly made
of platinum o r some other noble metal. Because noble-metal electrodes
are prone to surface poisoning and sometimes fail to achieve stable
potentials, potentioiiietric methods have not been widely used. According
 47

to Welz (1980), a patient,experienced analyst can produce valuable data

using noble metal electrodes.

Precision with potentiometric methods can be expected to be roughly

5% and is limited by the logarithmic (Nernstian) response of the electrode.
At low concentrations (ppb range), even a plot of log concentration vs
electrode potential is not linear. These methods are commonly used only
for “total oxidant,” as defined by the formation of 1 2 from I-, and all
chemical species that can participate in this reaction are included in
the analytical results. Standardization is based on sol.utions of known
iodine content, rather than standard chlorine solutions.

Because of relative ease of operation, potentiometry was used by

Eppley et al. (1976) for available chlorine measurements. The initial
electrode potential varied with the available chlorine concentration of
the sample and, after addition of potassium iodide solution at pB 4.0,
the potentials were stable. They concluded that the potentiometric method
has advantages of speed, sensitivity (10 u g / L ) , and can possibly be
adapted to on-line instrumentation (Eppley et al., 1976).

The Orion chlorine electrode instrument measures the redox potential

generated by the iodine produced by the reaction between available chlorine
and iodide at pH 4 . The electrode potential is a logarithmic function of
the iodine concentration and therefore proportional to the total available
chlorine concentration. The electrode consists of a platinum-sensing
electrode and an internal iodide reference. The instrument is small. and
portable, permitting rapid analysis at sampling sites. The calibration
curve of the electrode potential vs log of chlorine concentration is linear
from 0.05 t o 1.0 mg/L as chlorine. The approximate detection limit of this
potentiometric electrode is 50 ug/L chlorine (Sengupta et a l . , 1978).
Oxidizing agents ( e . g . , bromine, iodate, Cu(II), and b h O 2 ) interfere with
the measurement. Dissolved oxygen may also oxidize iodide to i o d i n e and
give erroneously high results f o r low-ppb concentration samples (Scarano
and Saroglia, 1980).

Seaman et al. (1980) evaluated a potentiometric electrode €or on-line

automated monitoring o € total chlorine in cooling-water effluents (fresh-
water). They concluded from both field and calibration data that the
 48

p o t e n t i o m e t r i c e l e c t r o d e measurements of t o t a l c h l o r i n e were s i g n i f i -
c a n t l y lower t h a n t h e Val-ues o b t a i n e d by amperometric t i t r a t i o n . The
i n s t r u m e n t s were c a l i b r a t e d by t h e m a n u f a c t u r e r . However ~ Olsoii and
Williams (1980), i n a c o m p a r a t i v e s t u d y of t h e amperometric t i t r a t i - o n
method and p o t e n t i o m e t r i c e l e c t r o d e method f o r d e t e r m i n i n g t o t a l a v a i l -
a b l e c h l o r i n e , concluded t h e v a l u e s o b t a i n e d by t h e two methods a t
d i f f e r e n t l a b o r a t o r i e s w e r e not s i g n i f i c a n t l y d i f f e r e n t (~‘0.05).

Helz (1980) s t a t e d t h a t a major d i f f i c u l t y i n low-level analysis

u s i n g t h e p o t e n t i o m e t r i c method is t h e c a l i b r a t i o n c u r v e s cease t o b e
l i n e a r below 50 u g / L ( i . e . , t h e s o l u t i o n s a t t h o s e c o n c e n t r a t i o n s do n o t
f o l l o w N e r n s e ’ s law). The n o n l i n e a r i t y r e q u i r e s g r e a t e r care i n c a l i -
b r a t i o n and s e d u c e s s e n s i t i v i t y . In addition, at ultralow concentrations
t h e t Line r e q u i r e d t o a c h i e v e e q u i l i b r i u m i n c r e a s e s s i g n i f i c a n t l y .

Rigdon e t a l , (1978) developed a computer-based s y s t e m t h a t compen-

s a t e s for t h e problems a s s o c i a t e d w i t h p o t e n t i o m e t r i c a n a l y s i s of u l t r a -
10t.r c o n c e n t r a t i o n s of o x i - d a n t s . They r e p o r t e d d e t e r m i n a t i o n s of c h l o r i n e
i n w a t e r i n t h e c o n c e n t r a t i o n r a n g e 3 t o 100 p g / I , w i t h an a c c u r a c y of
2 lig/L. The method u s e s O r i o n Model 97-70 c h l o r i n e e l e c t r o d e s and t h e
standard a d d i t i o n p o t e n t i o m e t r i c t e c h n i q u e t o measure t h e p o t e n t i a l . d i f -
f e r e n c e between t h e i-odide r e f e r e n c e e l e c t r o d e and i o d i n e t h a t i s g e n e r a t e d
by t h e a c t i v e c h l o r i n e , The t e c h n i q u e i s computer-autoniated t o p e r f o r m
t h e m u l t i p l e a d d i t i o n s of s t a n d a r d s , measure t h e p o t e n t i a l , and c a r r y o u t
t h e compucatioris t o d e t e r m i n e the c o n c e n t r a t i o n s of a c t i v e c h l o r i h e and
error functions. The method y i e l d e d Li.near c a l i b r a t i o n c u r v e s i n t h e con--
c e n t r a t i o n r a n g e 3 . 5 t o 35,000 pg/L. The method u s e s s t a n d a r d t e c h n i q u e s
of t h e a d d i t i o n of iodi.de t o a s s a y s o l u t i o n s a t pI-1 4 . The h y p o c h l o r o u s
a c i d and h y p o c h l o r i t e i o n c o n v e r t t h e i o d i d e t o i.odi-ne, and the p o t e n t i a l
d i f f e r e n c e between i o d i d e and i o d i n e i s measured. Consequently, o x i d i z i n g
a g e n t s such as bromine, i o d a t e , c u p r i c i o n , and manganese d i o x i d e i n t e r f e r e
w i t h t h e a s s a y because t h e y c o n v e r t i o d i d e t o i o d i n e . I n a d d i t i o n , oxygen
d i s s o l v e d i n t h e sample o r a b s o r b e d from t h e atmosphere can o x i d i z e t h e
i o d i d e and c o n t r : i b u t e s i g r i i f icant1.y h i g h r e s u l t s i n t h e a s s a y of low
microgram-per-liter r a n g e samples. A l s o , l o s s of g a s e o u s i o d i n e may occiur,
 49

resulting in erroneously low results. Thus it is desirable to minimize

the effect of oxygen oxidation of iodide and volatilization of the iodine
by operating under conditions where their magnitudes are comparable.
Rigdon et al. determined that the interference by oxygen in aerated water
was an average of 0.16 u g / L , with relative standard deviation of 0.1 p g / L
using their methodology. They studied the effect of stirring both gently
and vigorously and determined that these errors after stirring 6 min were
in the range of 0.6 and 20 ug/L chlorine, respectively. By standardizing
their measurement techniques and using computer calibration, they were
able to compensate for these errors. Another error that they evaluated
was air oxidation of the iodide reagents. Adding potassium iodide crystals
to the sample was a satisfactory means of correcting the problem of iodide
reagent oxidatLon. However, the initial potential varies with the amount
of iodide added. Therefore, the iodide concentration must be the same
f o r electrode calibration. Consequently, Ridgon and coworkers used R

reagent sample of 10% potassium iodide in 0.025 M sodium hydroxide and

determined that such reagent was stable for several weeks. They a l s o
evaluated the error due t o volatilization or l o s s of iodine gas and deter-
mined that this error was in the range of 0.04 to 0.064 after 6 min in
measurements of 10 to 80 pg/L chlorine using their standard methodology.
They determined that the lower limits of the assay is probably governed
more by absorption of oxygen than by the sensitivity of the chlorine elec-
trode (Rigdon et al., 1978).

3.3 Amperometry

Amperometry measures the current generated when a constant external

potential is applied across the indicator and reference electrodes. The
magnitude of the current is proportional to concentrations of dissolved
constituents which are oxidized and reduced at the electrode surfaces.
The current is generally measured on the diffusion-current region of the
current-voltage curve. In this region the current is independent of t h e
potential because of polarization of the indicator electrode. The con-
stituents reacting at the electrode surface are maintained at a concen-
tration near zero. Consequently, the current is limited by diffusion of
 50

the fresh reactants t o the electrode surface, The rate of diffusion and,
therefore, the current is proportional to the concentration of diffusing
substance in the solution (Willard et al.., 1965).

Several investigators have used amperometry to measure free and

total available chlorine in aqueous solution as summarized by Opresko
(1980). The current in an electrolytic cell is proportional to the oxi-
dants in solution if pH and temperature are held c o n s t a n t . Monochlor-
amine interferes with the free-chlorine analysis and electrode surface
contamination can contribute to instability and decrease in sensitivity
(Johnson, 1978). A common operating practice is to thoroughly rinse t h e
electrodes after the determination of total oxidant and p r i o r to the
determination of free oxidant t o reduce the effect of excess iodine
(adsorbed on the electrode surfaces) on the free oxidant measurement.

3.3.1 Chlorine-f&x monitor

Marienko and coworkers have developed a chlorine-flux monitor that

uses ainperometry to determine available chlorine and has an internal
coulometric iodine generator for periodic calibration. 'The system may
he used for continuous monitoring. Laboratory tests indicated that in
the range of 1.0 t o 100 p g / L chlorine the standard deviation was 1 vg/L.
Field tests were comparable to results achieved by amperometric titration
(Mari-enko,1976; Marienko et al. 1975, 1.976).

Sengupta et al. (1978) evaluated the chlorine-flux illonitor. They

determined a linear calibration curve for the coulometric-iodine generator
over the concentration range of 12 to 270 ug/L chlorine and estimated a
lower detection limit of 2 ug/T,. In the continuous mode of operation,
some difficulty was experienced with maintaini.ng constant flow rates,
Iodate, bromate, C u ( I I ) , Fe(II1) , and Mn(1V) interfered in this technique
l e s s than in the amperometric titration. The flux monitor calibration is
made on the samp1.e iiiatrix itself and, consequently, interferences are
minimized. The analytical data generated by Sengupta et al. (1978) showed
linearity for tapwater over the range 0 to 1.20 mg/L chlorine. They con-
cluded the instrument is potentially superior to other electrochemical
methods for o n s i t e chlorine analyses.
 Johnson et al. (1978) stated that continuous amperometric monitors
are much less selective for free chlorine than the amperometric titration
procedure. Morrow and Roop (1975) concluded that chloramines interfered
significantly (85%) in the techniques using normal bare-electrode ampero-
metric cells even when KI is not added.

3.3.2 Membrane electrode

Johnson and Edwards (1974) developed a membrane electrode for the

analysis of active halogen. They determined that a microporous fluori-
nated polymer permitted diffusion of molecular chlorine and bromine and
their hypohalous acids. Incorporation of this membrane into an ampero-
metric electrode permitted determination of these halogen species in
water solution. Johnson et al. (1978) stated that the interference from
combined available chlorine, monochloramine, and dichloramine was 1.3 t o
3.0%. A principal advantage of the membrane electrode, as cited by
Johnson ( 1 9 7 8 ) , i s that it is selective for HOC1.

Soderberg et al. (1980) compared free available chlorine analyses

using the membrane-covered polarographic electrode with the following
methods: amperometric titration, DPD-colorimetric, DPD-titrimetric
(DPD-FAS), and FACTS. The effect of sampLe concentration, pH, ionic
strength, temperature, and interferences on the different methods was
compared. The membrane-covered polarographic electrode has a limit of
detection greater than 50 y g / L as C 1 2 . Precision is -t2% and accuracy is
25% at 0.5 ppm. The membrane electrode was unresponsive to O C l - , mono-
chloramine, and ionic oxidants. It responded significantly to trichlor-
amine (%50% of the response to HOC1). It was also sensitive t o HOBr and
iodine, and thus could not be used directly for estuarine or saline water
applications. Soderberg et al. (1980) stated that the overall relative
standard error of the membrane electrode method compared to the standard
methods used in this test was <lo%. They stated that the overall stan-
dard error compared favorably to the precision and accuracy obtained for
free available chlorine analysis by Eishka and McFarren (1971) and
Nicolson (1965).
 52

3.4 Spectrophotometry

Opresko (1980) reviewed the use of ultraviolet spectrophotometry

to evaluate chemical speciation and degradation reactions of chlorine
and bromine compounds. These types oC studies have generally been
limited to laboratory rcscarch applications. For example, Baag
(1980 a,b) used ultraviolet absorbance spectra and measuremenrs in
his study on the formation of N-bromo-N-chloramines in chlorinated
saline waters.

Carpenter and coworkers developed a method using ultraviolet photo-

metric titration for determining total residual oxidant concentrations
in seawater. In this procedure, the water samples are treated at pH 2.0
with potassium iodide (2.4 x 10-'+M )..
... The oxidants are converted to 12,
which is detected as the I 3 complex ion by measuring the absorbance at
350 nm (Carpenter, 1.965;Carpenter et a ] . . , 1977; Carpenter and Macalady,
1978; Carpenter and Smith, 1.978). ?Iccording to Carpenter and Smith
(1978) the standard deviation (precision) for photometric titration of
replicate determinations was 2.5 l ~ g / Las chlorine, and the method appeared
t o be a viable alternative to amperometric titration. Interferences noted
were background levels of iodate which slowly reacted with the iodide t o
form iodine and l o s s of iodine by reaction with organic compounds
(Opresko, 1980). A s in other iodometric methods, it measures all strong
oxidants capable of oxidizing iodide.

3,5 Colorimetry

The principal advantages of colorimetric analysis of chlorine or

oxidant residuals are simplicity and convenience. Visual colorimetry,
however, is primarily useful f o r oxidant concentrations greater than
0.1 mg/L as chlorine. The color intensity at Amax of the oxidant reaction
products may be measured with simple hand-held c o l o r comparators or with
spectrophotometers. Colorimetric methods may suffer from interferences
caused by turbidity and natural organic coloring constituents (marine
gelbstoff) or humic compounds in the water being analyzed. This material
creates problems because its light absorbance changes on reaction with
chlorine, thus preventing the use of an unchlorinated control (blank).
 53

Although usually relatively unimportant at active chlorine concentration

above 0.1 mg/L (except in highly polluted water), this problem may be
significant at l o w to trace concentrations of chlorine, even in high-
quality waters.

3.5.1 Orthotolidine (OT) method

There is presently a trend away from orthotolidine methods because

(1) the indicator is a suspected carcinogen (Helz, 1980) and (2) the
acid-orthotolidine method is less accurate than other methods (Johnson,
1978; Standard Methods, 1975).

Acid-orthotolidine. Ellms and Hauser (1913) developed the ortho-

tolidine method as a substitute for the starch-iodide method. Because
of its simplicity, it has become the most widely and accepted colori-
metric method (White, 1972).

T h e acid-orthotolidine method is based on the oxidation of the color-

less benzidine compound, orthotolidine, to a highly yellow-colored holo-
quinone structure at low pH values (Marks, 1972). At slightly higher pH
values, the oxidation product is the blue unpaired elect-ron semiquinone
imine dimer (Johnson and Overby, 1969). If insufficient orthotolidine is
used, an unstable red holoquinone product is produced (Marks, 1972).

The yellow-colored complex i s formed in direct proportion t o c h l o r i n e

oxidant if the test is carried out at pH 1 . 3 or lower and with a ratio (by
weight) of three parts orthotolidine to one part chlorine (Chamberlin and
Glass, 1943; Palin, 1975). The total chlorine is measured by comparing
the color intensity of the test sample with color standards. This method
has been used primarily in the chlorine concentration range 50 p g / L to
10 mg/L. Nicolson (1965) reported the lower limit of detection of the
acid-orthotolidine method was 1.4 pg/L as determined by the concentration
calculated to produce an absorbance of 0.001. The molar extinction co-
efficient O F the acid-orthotolidine yellow reaction product is 5.03 x LO4
L mol'l cm-l as calculated from the Nicolson (1965) data.

Black and Whittle (1967b) observed that the orthotolidine colori-

metric test is unsatisfactory for the determination of free chlorine, and
 54

chloramines interfere in the test. According to Johnson (1978), the

yellow color of the orthotolidine oxidation product fades rapidly.
Nitrite and Fe(II1) interfere as well as Mn02, which interferes
stoichiometrically.

Details of the analytical procedures for the orthotolidine methods

are given by Marks (1972) and White (1972). It is not included in
Standard Methods (1975).

Orthotolidine-arsenite (OTA) method.

--_I_
Hallinan (1944) developed an
orthotolidine-arsenite (OTA) procedure designed to differentiate between
free chlorine (HOC1 and OCl-) and chloramine based on their di.ffe.rent
reaction rates with orthotolidine. Tn the OTA procedure, the water
sample containing available chlorine is reacted with orthotolidine, and
arsenite is added immediately, thus reducing the chloramines and thereby
preventing their development of additional color with the reagent. The
developed color is compared with a sample that has first been treated
with arsenite and subsequently reacted with orthotolidine. This control
permits compensation for (1) interfering suhstances such as manganese,
iron, o r nitrite, and (2) turbidity. The test does not completely eliminate
interference of monochloramine in the determination of the free-chlorine
residual.

According t o Hallinan (l944), the OTA test is restricted to the

following concentrations: chlorine, 3 mg/L; chloramine, 3 mg/L in the
test for chloramine and 25 mg/L in the test for chlorine; nitrite, satu-
rated solution of NaN02; iron, 25 mg/J., as PeCl3; and manganese, 2.5 mg/L
as colloidal Mn02. Below these limits, no false residuals were observed.
Temperatures had to be below 60°F (Connell, 1947) to avoid chloramine
interferences.

Sol10 and Larson (1965) stated that Lhe orthotolidine-arsenite (OTA)

test was probably the most widely used method for the determination of free
chlorine in water at that time. Chloramine interferences are minimized by
chilling the water sample to l0C.

Johnson (1978) stated that the free-chlorine test had a high combined-
chlorine (NH2C1) interference of 3 % / s at 2OoC. Nicolson (1965) found that
 55

below 100 pg/L c h l o r i n e , t h a t OTA s o l u t i o n d i d n o t obey Beer's l a w , t h u s

making t h e l o w e r l i m i t of d e t e c t i o n d i f f i c u l t t o d e t e r m i n e .

Details of a n a l y t i c a l methodology are g i v e n by Marks ( 1 9 7 2 ) , and

White (1972). T h i s method i s no l o n g e r i n Standard Methods (1975).

S t a b i l i z e d n e u t r a l o r t h o t o l i d i n e (SNORT) method. Johnson and Overby

(1969) d e v e l o p e d a n e u t r a l o r t h o t o l i d i n e method for f r e e c h l o r i n e i n which
t h e o r t h o t o l i d i n e and b l u e q u i n h y d r o n e imine p r o d u c t a r e s t a b i l i z e d by
bis(2-ethylhexy1)sulfosuccinate. The a u t h o r s s t a t e d t h a t c h l o r a m i n e i n t e r -
f e r e n c e i s minimized by m a i n t a i n i n g a n e u t r a l pH and t h a t i n t e r f e r e n c e by
i r o n and n i t r i t e i s e l i m i n a t e d . The r a t e of monochloramine i n t e r f e r e n c e
a t pH 7.0 w a s 40 L mo1-l rnin-'? and f i r s t o r d e r i n monochloramine and
o r t h o t o l i d i n e w i t h a f i r s t - o r d e r c a t a l y t i c dependence on hydrogen i o n
concentration. The dependence on hydrogen i o n (pH) e x p l a i n s why methods
of a n a l y s i s i n v o l v i n g lower pH, r e q u i r e d b e c a u s e of t h e i n s t a b i l i t y of
t h e chromogenic o x i d a t i o n p r o d u c t s , h a v e s i g n i f i c a n t c h l o r a m i n e i n t e r -
ference. Anionic s u r f a c e - a c t i v e a g e n t s s t a b i l i z e t h e c o l o r d e v e l o p e d by
f r e e c h l o r i n e and o r t h o t o l i d i n e a t pH 7.0. The optimum c o n c e n t r a t i o n of
A e r o s o l OT (bis(2-ethylhexyl)sulfosuccinate] w a s found t o be 0.4 ~g p e r
m i l l i l i t e r of s a m p l e p l u s r e a g e n t s (Stcfidazd Methods, 1975). The r a t i o
(by w e i g h t ) of o r t h o t o l i d i n e d i h y d r o c h l o r i d e t o c h l o r i n e must be a t Least
8 t o 1, and t h e pH between 6.5 t o 7.5.

.Johnson and Overby (1969) i n d i c a t e d t h a t the molar a b s o r p t i v i t y a t

Xmaw 625 nm of t h e b l u e q u i n h y d r o n e imine w a s 3 . 4 1 x l o 4 L rno1-l cm-I a t

pH 7.0. Thus t h e s e n s i t i v i t y ( d e f i n e d as t h a t c o n c e n t r a t i o n p r o d u c i n g
0.001 a b s o r b a n c e p e r cm) of SNORT i s 2 . 1 pg/L as c h l o r i n e . They found
t h e r e l a t i v e s t a n d a r d d e v i a t i o n w a s 0.39% f o r 10 measurements a t 0.98
mg/L c h l o r i n e and remained good up t o 7 mg/L c h l o r i n e . Johnson and Overby
(1969) r e p o r t e d t h e i n t e r f e r e n c e of combined c h l o r i n e i n t h e E r e e - c h l o r i n e
a n a l y s i s by t h e SNORT method t o b e l o w ( i . e . , O . l % / m i n i n t e r f e r e n c e by
NB2C1). The b l u e c o l o r f a d e s slowly, f o r example, a t 25°C and 0.7 mg/L
c h l o r i n e , f a d i n g p r o d u c e s a n e r r o r of %O.l%/rnin. A t h i g h e r t e m p e r a t u r e s ,
f a d i n g i s more r a p i d (Johnson and Overby, 1 9 6 9 ) . Manganese d i o x i d e i n t e r -
feres stoichiometrically with the f r e e chlorine analysis. They found no
m e a s u r a b l e i n t e r f e r e n c e due t o d i c h l o r a m i n e (NHC12) u:) t o M.
..- Fe(IT1)
 56

up t u PI
- and nitrite up to 2 x M
- did not interfere. Standard
P4ethods (1975) reports that the minimum detectable concentration of SNORT
is 10 ug/L free chlorine. Details of analytical methodology are given in
StandByd Met-hods (1975).

3.5.2 N,N-Diethyl-p-phenylenediamine (DPD) methods

__.

Palin (1957) described a method for analysis of free chlorine, mono-

chloramine, dichloramine, and nitrogen trichloride using N,N-diethyl-p-
phenylenediamine (p-aminodiethylamiline) as the indicator. A t neutral pH
( 6 . 2 to 6.5), DPD gives a red color (Amax 515 nm) on reacting with chlorine.
Addition of a small amount of KI causes monochloramine to react with the
iodide, producing free I7 which forms a red color. Further addition of
KI causes a reaction of dichloramine without pH adjustment. Nitrogen
trichloride is included in the dichloramine f r a r t i - o n but may a l s o be in-
cluded with the free-chlorine fraction by changing the order of reagent
addit io11.

In the DPD colorimetric method, the solutions are compared against

standard color solutions prepared from potassium permanganate after the
several analytical steps (Opresko, 1980). T o avoid interfering reactions,
colorimetric measurements must be made immediately after the free-chlorine
and monochloramine steps. For the slower dichloramine reaction step, a
period of 2 min is required (White, 1972).

Several significant problems are associated with the DPD methods:

(1) the DPD reagent is not very stable in aqueous solution [i.e., dis-
coloration occurs on standing (Palin, 1957; Johnson, 1978; Sengupta et al.. ,
19781, and (2) the oxidized colored products show fading within a few
minutes. The color developed with DPD is also reported to be temperature
sensitive (Palin, 1957; Marks et al., 1.951; SengupCa et al. ~ 1978).

Manganese(1V) interferes with free-chlorine measurements but may be

corrected for by separate tests according to Palin (1957). However, Johnson
(1978) states manganese dioxide interferes stoichiometrically in the free-
chlorine measurement. Interferences from Fe(II1) and nitrite are minimal
(Sol10 and Larson, 1965). Copper and nitrite will interfere with dichlor-
amine measure~nents. Dissolved oxygen causes faint col-or development w i t h
 57

time [e.g., fully saturated water at 18OC gave an error of 10 lig/T, as

free chlorine (Palin, 1957)]. Interference by copper up to 10 mg/L is
overcome by incorporating ethylenediaminetetracetic acid (EDTA) into the
reagents. The EDTA enhances the stability of the DPD solution by (1) re-
tarding oxidation, and (2) suppressing (almost completely) the dissolved
oxygen errors by preventing trace metal catalysis (Standard Me-thnds,
1975).

Johnson and Overby (1969) reported that the combined chlorine

(NHZC1) interference in the DPD free chlorine measurement is 3.6X/min at
25OC. Because monochloramine slowly reacts with the DPD reagent (mono-
chloramine breakthrough), Palin (1957) emphasizes that readings must be
taken rapidly.

The DPD method has been most recently evaluated by Sengupta et al.
(1978). They concluded that for measurement in distilled water or water
with low interference the DPD concentration, temperature, and pH have
limited effects on the analytical response. However, with monochloramine
present, temperature and pH will have a significant effect. Serious
errors can be caused by reagent instability. Using fresh DPD solutions
at pH 6 minimized drift error. In the presence of iodide, the compounds
103 , Cu(II), F e ( L I I ) , S208’-, and H 2 0 2 were shown to cause DPD c o l o r
development. Bromate did not interfere.

Nicolson (1965) found the DPD colorimetric method to be the most

accurate of the nine older colorimetric methods he evaluated for solutions
containing free and combined chlorine.

Nicolson (1965) reported a sensitivity or lower limtt of detection

for the DPD-colorimetric method of 4 ug/L chlorine, and for the DPD-
titrimetric, 11 pg/L chlorine. Sengupta et al. (1978) reported a 116 pg/L
lower detection limit with the DPD-colorimetric method and estimated that
a 5 ug/L lower limit could be achieved with instrument modifications.
Johnson reported the molar extinction coefficient (e) of the DPD reaction
product was 7.5 x lo3 L mol-’ cm-I (Johnson, 1981). Therefore, using this
value, the calculated lower limit of detection is 9.5 pg/L.
 58

R e c e n t l y P a l i n (1978, 1980) h a s added a s t e p t h a t d e c r e a s e s t h e

i n t e r f e r e n c e of monochloramine d u r i n g t h e f r e e - c h l o r i n e measurement
u s i n g t h e DPD-colorimetric p r o c e d u r e . The s t e p i n v o l v e s t h e immediate
a d d i t i o n of t h i o a c e t a m i d e a f t e r DPD has been added t o t l r e sample. This
a p p e a r s t o a c t i n two b e n e f i c i a l ways t o i n c r e a s e t h e s e l e c t i v i t y of t h e
procedure: (1) t h e t h i o a c e t a m i d e immediately r e d u c e s any combined
c h l o r i n e p r e s e n t , b u t t h e f r e e r e s i d u a l w i l l have a l r e a d y r e a c t e d w i t h
t h e DPD r e a g e n t b e c a u s e of i t s r a p i d r e a c t i o n r a t e ; ( 2 ) t h i o a c e t a m i d e
reverses t h e monochloramine-DPD r e a c t i o n . The r e a c t i o n reversal i s
s e l e c t i v e f o r monochloramine b e c a u s e when DPD i s o x i d i z e d by f r e e c h l o r i n e
t h e a d d i t i o n of t h i o a c e t a m i d e h a s no e f f e c t on t h e c o l o r r e a c t i o n p r o d u c t
(Snead e t a l . , 1 9 8 1 ) .

A n a l y t i c a l m e t h o d o l o g i e s a r e g i v e n i n d e t a i l i n Standard Msthods
(1975). The DPD-colorimetric method h a s b e e n approved by EPA f o r a n a l y s i s
of c h l o r i n e i n water samp1e.s (FederaZ R e y i k t w , 1976).

3.5.3 Leuco c r y s t a l . v i o l e t (LCV) method

Black and W h i t t l e (1967b) developed a n a n a l y t i c a l method f o r sepa-

r a t e l y measuring f r e e and t o t a l a v a i l a b l e c h l o r i n e u s i n g l e u c o c r y s t a l
v i o l e t , 4 , 4 ' ,4"-methylidynetris(N-lV-dimet~hylaniline) e The c h l o r i n e o x i d a n t s
are d e t e r m i n e d by v i s u a l comparison of t h e b l u e - c o l o r e d o x i d a t i o n p r o d u c t
w i t h t h e c o l o r d e v e l o p e d by c h l o r i n e s t a n d a r d s o r by r e f e r e n c e t o a s t a n -
dard c a l i b r a t i o n curve. The combined a v a i l a b l e c h l o r i n e i s d e t e r m i n e d by
tht? d i f f e r e n c e between measurements f o r t h e f r e e c h l o r i n e and t h e t o t a l
a v a i l a b l e c h l o r i n e (Standard Methods, 1 9 7 5 ) .

The i n d i c a t o r s o l u t i o n p r o p o s e d by Black and W h i t t l e (1967b) c o n s i s t s

of a d i l u t e l e u c o c r y s t a l v i o l e t s o l u t i o n and a s a t u r a t e d mercury(1Z)
c h l o r i d e s o l u t i o n which enhances c o l o r development and r e t a r d s d i c h l o r -
amine i n t e r f e r e n c e (Black and Whittle, 1 9 6 7 a ) - F r e e - c h l o r i n e measure-
ments i n t h e r a n g e of 0 . 1 t o 2 mg/L are made a t p H 4 by me.iruring t h e
a b s o r b a n c e of t h e d e v e l o p e d c o l o r a t Amax, 592 1-1111, Total available
c h l o r i n e measurements are made by a d d i n g K I t o t h e sample b e f o r e c o l o r i -
m e t r i c d e t e r i n i n a t i o n (Black and Whittle, 1967b). P r o p e r c o l o r development
i s dependent upon pH ( 3 . 6 t o 4 . 3 ) , r a t i o of i n d i c a t o r t o o x i d a n t
 59

(130:l by weight), sample temperature ( < 4 0 ° C ) , and the proper timing

(test must be completed within 5 min) ( S t a n h d Methods, 1975).

The indicator reacts rapidly with free chlorine but only slowly
with combined chlorine (Opresko, 1980). Johnson (1978) indicated that
the monochloramine interference is only l.O%/min in the free-chlorine
analysis. Interference from chloramines in free-chlorine determinations
is minimized if measurements are completed quickly. Interference from
iron and nitrate up to 20 mg/L is negligible. Alkalinity values up to
150 mg/L and total hardness up to 300 mg/L did not interfere. Chloride
concentration over 600 mg/L gave lower absorbance values. Manganese(1V)
interferes at very low concentrations (Black and Whittle, 1967b). Johnson
(1978) indicates MnOz interferes stoichiometrically in the free-chlorine
measurement.

This procedure has not been widely used for routine analyses due to
the large number of reagents and complex mixing procedure (Palin, 1975;
Johnson, 1978; Opresko, 1980). However, the procedure i s accurate and
suppresses the hydrolysis (interference) of organic chloramines (Lishka
et al., 1969). Whittle and Lapteff (1975) reported a modified LCV method
for determining total available chlorine, free available chlorine, mono-
chloramine, dichloramine, and nitrogen trichloride.

The minimum detectable concentration by the LCV method is 10 p g / L

free available chlorine and 5 vg/L total available chlorine (Standayd
Mm%ds, 1975).

Details of the analytical methodology are presented in Stcxndayd

Methods (1975) and Marks (1972).

3.5.4 Methyl orange- method

~ -

S o l l o and Larson (1965) reported a procedure based on the quantitative

bleaching of methyl orange by free chlorine. The oxidant concentration is
determined by measuring the change in absorbance of the solution at 510 nm.
At pH 2, the test is specific for free chlorine, and chloramine interference
is minimized by measuring the absorbance in .C2 min. Chloramine interference
is increased by bromide and, also, by concentrations of chloride >500 mg/L.
Maiiganese(1V) q u a n t i t a t i v e l y i n t e r f e r e s . The c o n c e n t r a t i o n of M n ( 1 V ) may
b e d e t e r m i n e d by m e a s u r i n g the b l e a c h i n g of a c o n t r o l sample i n wh-ich the
Eree c h l o r i n e h a s been reduced by a r s e n i t e . I n t e r f e r e n c e s of F e ( I I 1 ) and
n i t r i t e up t o 1 0 mg/L are n e g l i g i b l e . (Sol-lo and T>arson, 1965; Standard
!&&hods, 1975; Opresko, 1 9 8 0 ) .

The m e t h y l orange method, because i t depends on b l e a c h i n g r a t h e r t h a n

col-or development, r e q u i r e s p r e c i s e measurement of r e a g e n t s and p r e c i s e
c o n t r o l of t e m p e r a t u r e (Sol10 and L a r s o n , 1 9 6 5 ) . F o r t h i s r e a s o n and be-
c a u s e t h e method l a c k s i n p r e c i s i o n , i t : i s 110 l o n g e r i n c l u d e d i n St(n2dai.d
Methods (1975). N i c o l s o n (1965) e x c l u d e d t h e methyl o r a n g e method from
h i s c o m p a r a t i v e s t u d y b e c a u s e i t gave (1) n o n l i n e a r c a l i b r a t i o n c u r v e s ,
and ( 2 ) t h e order and rate of mtxing t h e r e a g e n t and sample a f f e c t e d t h e
e x t e n t of b l e a c h i n g .

Details of t h e a n a l y t i c a l method are g i v e n by Sol.10 arid Larson (1.965).

3 " 5.5 S y r i n g a_
l d-a -z i.n-e~ (FACTS) method

The s y r i n g a l d a z i n e test f o r f r e e c h l o r i n e was d e v e l o p e d by Bauer and

Rupe (1971) and m o d i f i e d by Cooper e t a l , (1.975). A t pEI 7 s y r i n g a l d a z i n e
r e a c t s w i t h f r e e c h l o r i n e t o produce a r e d c o l o r (A, 530 nm), b u t i t
i s v e r y i n s e n s i t i v e t o chlorainines. 'The p r e c i s i o n ( r e p r o d u c i b i l i t y ) of
the test was good, w i t h r e l a t i v e s t a n d a r d d e v i a t i o n s r a n g i n g from fl t o
k20% f o r c o n c e n t r a t i o n s h a v i n g from 1.055 t o 0.055 mg/L c h l o r i n e , respec-
tively, Tn a series of tests w i t h t a p water, the r e s u l t s o b t a i n e d by (:lie
s y r i n g a l d a z i n e method compared v e r y c1osel.y w i t h t h o s e o b t a i n e d by b o t h
the o r t h o t o l i . d i n e t e s t and o r t h o t o l i d i n e - a r s e n i t e tests. The c o l o r de-
v e l o p e d i n t h e t e s t i s maxiinurn a f t e r 30 s a t p H 7 and i s s t a b l e f o r a t
l e a s t 5 min f o r c o n c e n t r a t i o n s < 5 mg/L c h l o r i n e . A t h i g h c h l o r i n e concen-
t r a f l i o n s , c o l o r fadi.ng i s o b s e r v e d (Cooper e t a l . , 1 9 7 5 ) .

G u t e r e t a l . (1972) and S o r b e r e t a l . (1977) e v a l u a t e d several

a n a l y t i c a l methods and concluded t h a t thc IjPD method was most a c c u r a t e
and p r e c i s e , b u t t h e s y r i n g a l d a z i n e method w a s most s p e c i f i c f o r f r e e
c l ~ l o r i m ~Thus t h e y developed a m o d i f i e d method c a l l e d FACTS ( f r e e n v a i l -
a b l e c h l o r i n e t e s t w i t h s y r i n g a l t l a z i n e ) d e s i g n e d f o r two r a n g e s of f r e e
chlorine: FACTS I , t o 5 rng/L; FACTS 11, t o 1 0 mg/T, (Cooper e t al., 1 9 7 5 ) .
 61

In the FACTS method, very high concentrations of monochloramine

(>35 mg/L), oxidized manganese (>2.6 mg/L), and ferric iron ( > l o mg/L)
will produce color but at a slow rate. Nitrite, nitrate, sulfate, and
chloride (21 g/L) do not interfere (Standard Methods, 1975). Bromine,
bromamines, iodine, and ozone will react with syringaldazine (Sengupta
et al., 1978; Ryan et al., 1980). Consequently, this method like a l l
others would not be specific for free available oxidants in seawater.

Lieberman et al. (1978, 1980) modified the FACTS procedure to yield

a colorimetric method for the analysis of total chlorine, total combined
chlorine, and the various forms of combined chlorine. The reactions of
the various forms of free and combined available chlorine with potassium
iodide are quantitative at pH 4 and can be used for FACTS analysis o f
total available chlorine. Efforts at differentiating between mono- and
dichloramine by pH adjustment of the potassium iodide reaction were un-
successful. Beers law data obtained with this method demonstrate that
the reaction is linear in the range 0.2 to 10 mg/L as chlorine. Color
development occurred in .<1
min, and fading was appreciable only at high
chlorine concentration. The method was shown to be simple, accurate,
and precise for analysis of total available chlorine.

Standard Methods (1975) reports the FACTS procedure is sensitive to

free available chlorine concentrations of 50.1 mg/L. Sengupta e t al.
(1978) reported a lower limit of detection of 12 u g / L using a spectro-
photometer with a 1-cm length but that the lower practical limit could
be extended to 5 vg/L with a 10-cm path length. Johnson (1981) reported
the molar extinction coefficient (E) of the syringaldazine reaction pro-
duct is 2.3 x lo4 L mold1 cm-’. Therefore, the calculated lower limit
of detection is 3.1 I.rg/L.

Details of analytical methodology are given in Standard Methods

(1975).

3.5.6 Cyanogen chloride-barbituric acid method

Nicolson (1965) concluded that the cyanogen chloride-barbituric

acid method was most: selective of the colorimetric methods evaluated for
 62

t h e measurement of f r e e c h l o r i n e i n t h e a b s e n c e of c h l o r a m i n e s . In this
method H O C l reacts w i t h c y a n i d e i o n t o form cyanogen c h l o r i d e which, i n
tiurn, reacts w i t h p y r i d i n e by opening t h e r i n g t u f o r m a d i a l d e h y d e . The
d i a l d e h y d e reacts w i t h an amine t o produce a n i n t e n s e l y c o l o r e d a n i l e ,
t h e c o l o r i n t e n s i t y of which p r o v i d e s a q u a n t i t a t i v e measure of t h e rree
c h l o r i n e (Marks, 1 9 7 2 ) . Although amines s u c h as b e n z i d i n e and s u l f a n i l i c
a c i d have been u s e d , b a r b i t u r i c a c i d h a s g i v e n b e t t e r r e a g e n t s t a b i l i t y ,
s e n s i t i v i t y , and r e l i a b i l i t y . The method i s c o n s i d e r e d v e r y s p e c i f i c f o r
free chlorine.

N i c o l s o n (1965) found llhe cyanogen c h l o r i d e - b a r b i t u r i c a c i d method

t o be virtua1.l.y f r e e from s e r i o u s i n t e r f e r e n c e . In t h i s t e s t , Mn(II1) a t
0 . 5 mg/L ( a s c h l o r i n e ) was d e t e c t a b l e as 0.01 mg/L. Bromine i n t e r f e r e d
partially. The l i m i t of d e t e c t i o n was 0.6 p g / L f r e e c h l o r i n e . The rela-
t i v e s t a n d a r d d e v i a t i o n ( p r e c i s i o n ) w a s 3,5% and 1.8% f o r f r e e c h l o r i n e
c o n c e n t r a t i o n s of 0 . 1 and 0.5 m g / L , r e s p e c t i v e l y . The method i s r e p r o -
d u c i b l e , s e n s i t i v e , r e l a t i v e l y s p e c i f i c , and i n d e p e n d e n t of t e m p e r a t u r e .
However, t h e r e a g e n t w a s found t o be u n s t a b l e i n s t o r a g e , and t h e method
had the d i s a d v a n t a g e s of (1) r e s p o n d i n g o n l y p a r t i a l l y t o combined
c h l o r i n e ; and ( 2 ) b e i n g a complex p r o c e d u r e , t h u s r e s t r 2 c t i n g i t s p r a c -
t i c a l . use (Nicolson, 1965).

3.6 Chemiluminescence

The o x i d a t i o n of l u m i n o l (5-amino-2,.3-dihydrophthalazine-l,&-dione)
i s accompanied by i n t e n s e b l u e chemiluminescence ( S e i t z , 1 9 7 5 ) . Isacsson
and Wetterraark (1976, 1978) have used t h i s r e a c t i o n t o d e v e l o p a v e r y
s e n s i t i v e a n a l y t i c a l method f o r IIOC1. Isacsson e t as. (1978) p o s t u l a t e d
t h a t b o t h HOC1 and C12(aq) o x i d i z e l u m i n o l t o a z a q u i n o n e and produce a
sl.ow and r a p i d l i g h t emi.ssion, r e s p e c t i v e l y . They concluded t h a t MOCl
w a s t h e r e a c t i n g s p e c i e s a t pH 8.9 t o 1 1 . 5 , and t h e p s e u d o - f i r s t - o r d e r
ra[:e c o n s t a n t f o r t h e o x i d a t i o n of l u m i n o l by H O C l w a s a p p r o x i m a t e l y
lo2 s-1.

The chemiluminescence r e a c t i o n i s conducted a t a l k a l i n e pH by mixing

t h e l u m i n o l s o l u t i o n (5.5 x lom3-
M i n 0.01 M NaOH) , c a r b o n a t e buffer, and
I

aqueous c h l o r i n e s o l u t i o n . Emitted l i g h t , Lax,425 nm, i s measured by

 63

a fibre optics-photomultiplier-recorder system. Hydrogen peroxide may

be used to intensify the light emission (optimum concentration, 3 . 4 x
H202). Luminol shows chemiluminescence only in an alkaline environment.
The optimum pH €or maximum light intensity from the hypochlorine-luminol
reaction is 8.9 (Isacsson and Wettermark, 1976, 1978; Isacsson et aL.,
1978). Isacsson arid Wettermark (1976) determined a linear calibration
curve in the hypochlorire concentration range to M.
I
In a
set of eight measurements, the relative standard deviation (precision) of
free chlorine at M
- was 6%. A principal difficulty in measurements
of 0.05 ng hypochlorite or less was the instability of the chlorine
solution.

The chemiluminescence method has much potential for ultralow-level

detection of free chlorine but has received very limited application in
the water treatment field (Hall et al. 1981.).

3.7 Titrimetry

In contrast to the analytical methods that are based on direct

measurement of some property of the total oxidants or an induced c o l o r i -
metric or chemiluminescence property, the titrimetric methods (by
definition) involve the reaction of the oxidants with a reducing reagent
that is added to the sample to the exact extent required to just com-
pletely react with the sample constituents. An important parameter in
these methods is the choice of a technique for sensing the progress of
the titrimetric reaction and estimating when the equivalence p o i n t has
been reached. The reaction equivalence point may not be identical with
the titration "endpoint," and this discrepancy becomes more significant
in analyses f o r low concentrations (<l mg/lA) of total oxidants.
Potentiometry, amperometry, spectrophotometry, or visual colorimetry
may be used to follow the course of the titration. Given adequate
sensitivity for the endpoint detection, titrimetric methods are in-
herently precise since it i s relatively simple to measure the volume
of the titrating solutfon with a precision better than 1%.
 64

3.7.1 lodome t r i c
____.._._- method

The r e a c t i o n of i o d i - n e w i t h t h i o s u l f a t e ,

i s one of t h e most i m p o r t a n t i n c h e m i c a l a n a l y s i s and i s u s e d i n a n a l y s e s

For a v a r i e t y of s u b s t a n c e s . It p r o v i d e s a g e n e r a l method f o r t h e d e t e r -
m i n a t i o n of o x i d i z i n g a g e n t s by t h e a d d i t i o n of e x c e s s i o d i d e and
t i t r a t i o n of t h e r e s u l t i n g i o d i n e w i t h t h i o s u l f a t e . Soluble s t a r c h is
used as a n e n d p o i n t i n d i c a t o r f o r t h i s t i t r a t i o n , g i v i n g a deep b l u e c o l o r
as l o n g as a n " a p p r e c i a b l e ' l c o n c e n t r a t i o n of i o d i n e i.s p r e s e n t ( L a t i m e r
and Wildebrarid, 1940). It s h o u l d be r e a l i z e d t h a t t h i s s t a t e m e n t a p p l i e s
t o t i t r a t i o n s of f a i r l y h i g h c o n c e n t r a t i o n s , f o r example, i n t h e s t a n -
d a r d i z a t i o n oE s o l u t i o n s ; b u t f o r v e r y d i l u t e s o l u t i o n s t h e v i s u a l e n d p o i n t
i s r e a c h e d c o n s i d e r a b l y i n advance of t h e e q u i v a l e n c e p o i n t . Also, s i n c e
i t measures a l l r e a g e n t s c a p a b l e of o x i d i z i n g i o d i d e , i t i s i n h e r e n t l y
lacking i n selectivity.

When c h l o r i n e w a s f i r s t used f o r w a t e r t r e a t m e n t , t h e o n l y method

a v a i l a b l e f o r a n a l y s i s o f f r e e and combined a v a i l a b l e c h l o r i n e was t h e
i o d o m e t r i c ( s t a r c h - i o d i d e ) method (White, 1972). The method i s b a s e d on
t h e p r o d u c t i o n by c h l o r i n e of f r e e i o d i n e from p o t a s s i u m i o d i d e s o l u t i o n s
a t pH 8 o r less ( p r e f e r a b l y pH 3 t o 4 ) . The i o d i n e i s subsequent1.y
t i t r a t e d w i t h a s t a n d a r d s o l u t i o n of sodium t h i o s u l f a t e w i t h s t a r c h as
the indicator. T i t r a t i o n a t n e u t r a l pH minimizer; i n t e r f e r e n c e from
Fe(III), P h ( I V ) , and n i t r i t e ; b u t t i t r a t i o n a t a c i d i c pN i s n e c e s s a r y
f o r accurate determination of t o t a l a v a i l a b l e chlorine. For a n a l y s i s of
w a s t e w a t e r s o r waters c o n t a i n i n g r e l a t i v e l y hi.gh c o n c e n t r a t i o n s of o r -
g a n i c s , a s t a n d a r d r e d u c i n g a g e n t i s added t o r e a c t w i t h t h e o x i d a n t
s p e c i e s i n s t o i c h i o m e t r i c excess and t h e u n r e a c t e d r e d u c i n g a g e n t i s
"back-titrated" with a srandard oxidant. T h i s method a v o i d s I.oss of
i o d i n e through r e a c t i o n s w i t h o r g a n i c s . F o r a n a l y t i c a l methodology
details refer to Standard Methods (1.975) and Annual Book of AS2'M Standards
(1976). 'The i o d o m e t r i c method w i t h s t a r c h - i o d i n e o r amperometric e n d p o i n t
d e t e c t i o n h a s been approved by EPA f o r a n a l y s i s of c h l o r i n e i n w a t e r
s o l u t i o n (Federal R e g i s t e r , 1 9 7 6 ) .
 65

It should be noted that all the analytical methods for free or com-
bined oxidants require standards or reference solutions of known strength
for calibrations of the measuring system. Commonly, commercial hypo-
chlorite solutions (household bleach) are used, and iodometric titrations
with the visual starch endpoint indicator are a convenient method for
assaying the strength of these materials. Since errors in this assay
will be reflected in all the data collected with whatever method is
calibrated with the “standard” solutions, high confidence that this step
has negligible errors is quite important.

Hallinan and Thompson (1939) studied in detail the influence of pH

over the range 1 . 3 to 7.47 and iodide concentration over the range of 0.1
to 1.25 g/L on the titration of total available chlorine and evaluated
the effects of certain interfering substances such as manganese. They
determined that the reaction stoichiometry was affected by increasing pH.
At lower pH, iodine reacts with thiosulfate to form iodide and tetra-
thionate ion [reaction ( 5 ) ] . At higher pH values, however, tetrathionate
ion may be further oxidized by iodfne to sulfate [reaction (6711.

Increasing iodide concentration partially suppresses this reaction. The

slower the titration is performed, the more sulfate is formed, with cor-
respondingly lower chlorine titer. The effect of increasing pH is to
reduce Mn(1V) interference. The authors present a nomogram of pH, time,
and K I concentration to permit optimization of the thiosulfate titration.

Carpenter (1965) listed several sources of error in iodine titrations

using thiosulfate: (1) air oxidation of iodide, (2) volatilization of
iodine, ( 3 ) oxygen contributed by the reagent solution, ( 4 ) iodate con-
tamination of the iodide solutions, (5) consumption o r production of
iodine by reagent contaminants, and (6) difference between titration
endpoint and the equivalence point. In iodine titration with thiosulfate,
he indicated that air oxidation of iodide to iodine is minimized by using
pH of 2 o r greater and that the l o s s of iodine by volatilization was mini-
mized by the formation of the triiodide complex with h i g h iodide concen-
trations. The error produced by iodate contamination o f the iodide reagent
 66

could be reduced by c a r e f u l s e l e c t i o n of c h e m i c a l s . Reducing i m p u r i t i e s

i n t h e i o d i d e r e a g e n t nay c o n t r i b u t - e t o a n e g a t i v e b l a n k . Such i m p u r i t i e s
were caused by d a r k and d i s c o l o r e d p a r t i c l e s i n the sodium i o d i d e reagenL
and were removed m a n u a l l y by u s i n g t w e e z e r s and a hand l e n s .

The i o d o m e t r i c ( s t a r c h - i o d i d e ) p r o c e d u r e i s u s e f u l o n l y i n d e t e r -
mining t o t a l a v a i l a b l e c h l o r i n e . Standard Methods (1975) gi.ves t h e
minimum d e t e c t a b l e c o n c e n t r a t i o n as 40 pg/L.

Iodometry forms t h e b a s i s f o r t h e amperometric t i t r a t i o n and o t h e r

t o t a l o x i d a n c a n a l y s i s methods d i s c u s s e d b e 1 . 0 ~ . The s e n s i t i v i t i e s of
several i o d i n e e n d p o i n t t e c h n i q u e s , as i n d i c a t e d by C a r p e n t e r (1965),
were v i s u a l s t a r c h , 1 0 m i c r o e q u i v a l e n t s / L (350 ug/L as Cl); c o l o r i m e t r i c
s t a r c h , 2 microequival.ents/L (70 u g / L as C l ) ; amperometric t e c h n i q u e ,
0.02 microequivalent/T> (0.7 ug/L as C 1 > i n 0.001 _._.
N i o d i d e or 0.08
microequivalent/L (2.8 ug/L as C l ) i n 1 -
N i o d i d e ; u l t r a v i o l e t absorp-
t i o n a t 350 nm, 0.015 m i c r o e q u i v a l e n t / L ( 0 . 5 iig/L a s Cl) ihi 0.01 -
N
iodide.

3.7.2 Amperometric t i t r a t i o n

Amperometric t i t r a t i o n i s performed by o b s e r v i n g changes i n t h e

c u r r e n t as t h e t i t r a t i o n p r o c e e d s . The e l e c t r o d e p o t e n t i a l i s n o t v a r i e d
during the t i t r a t i o n . The e n d p o i n t i s b e s t determined g r a p h i c a l l y ,
a l t h o u g h i t i s sometimes i n d i c a t e d by a nonmeasured a b r u p t c u r r e n t i n -
c r e a s e or d e c r e a s e ( S t o c k , 1 9 6 5 ) .

'The amperometric t i t r a t i o n method i s current1.y p r e f e r r e d € o r p r e c i s e ,

low-level a n a l y s e s of a v a i l a b l e c h l o r i n e ( H e l z , 1 9 8 0 ) ; Sengupta e t a l . ,
1978; H a l l e t a l . , 1981; Opresko, 1980; Bender, 1978; U t i l i t y Water
A c t Group, 1 9 7 9 ; Rice e t al., 1980; Brooks and S e e g e r t , 1979; Payne,
1979; Sugam e t a l . , 1 9 8 1 ; Olson and W i l l i a m s , 1980; Scarano and
S a r o g l i a , 1980). Marks and Glass (1942) p i o n e e r e d i n t h e development
of amperometric t i t r a t i o n f o r c h l o r i n e r e s i d u a l a n a l . y s i s , and many i n -
v e s t i g a t o r s have c o n t r i b u t e d t o i t s development ( H a l l e r and L i s t e k , 1.948;
Marks e t a].., 1951; Morrow, 1 9 6 6 ; Manabe, 1974; Morrow and Roop, 1975;
Sengupta e t a l . , 1978; Brooks and S e e g e r t , 1 9 7 9 ) . S t a n d a ~ dMethods (1975)
 67

presents accepted analytical methodology details. In general, the standard

amperometric titration method is based on the titration of free chlorine or
iodine by a standard solution of phenylarsineoxide (or sodium arsenite),

where X = chlorine, bromine, or iodine ( H e l z , 1980).

This titrant can be used a l s o to advantage in the visual starch iodo-

metric titration. Marks et al. (1951) modified the method to permit dif-
ferentiation between the various oxidant species based on their ability to
react with phenylarsine oxide (PAO) or iodide. In nonsaline waters, only
free oxidant is reduced directly to PA0 at pW 7. Monochloramine reacts
wSth KI to form I2 at neutral pH, which is titrated by PAO. 1)ichloramine
reacts with KI to form I2 at pH 4 . If present, nitrogen trichloride will.
titrate partly as free chlorine and partly as dichloramine. Thus by ap-
propriate adjustment of pH and addition of KI, free chlorine, free chlorine
plus monochloramine, and total chlorine residuals may be determined.

The application of this method to seawater analyses is being investi-

gated ( H e l z , 1980; Carpenter et al., 1977; Sengupta et al., 1978).

A s currently developed, the lower limit of detection by amperometric

titration is 1.5 ug/L in estuarine waters ( H e l z , 1980) and 1.8 vg/T. in
freshwater (Brooks and Seegert, 1979). According t o Helz (19881, this is
approximately one order of magnitude lower than the detection limit of
standard commercial titrators. For example, the detection limit f o r one
standard commercial amperometric titrator is 20 pg/L. Sengupta et al.
(1978), Sugam et al. (19811, and Brooks and Seegert (1979) presem
details concerning ultralow available chlorine analyses with amperomctric
ti tration.

Manabe (1974) indicated that the primary disadvantages of ampero-

metric titration are (1) l o s s of chlorine during analysis due to photo-
decomposition or volatilization, and ( 2 ) incomplete reaction of the PA0
with the chlorine residual. He determined that Cu(I1) at concentrations
as low as 50 pg/L gave a false chlorine residual and reduced analytical
 68

sensitivity by poisoning the electrode. Iron(II1) at 5 mg/L caused a

similar loss in sensitivity. Manganese oxide does not interfere w i t h
free-chlorine determinations, and monochloramine had only a l o w inter-
ference [i-e., O.l%/min, Johnson (l978)]. Free chlorine apparently
causes a film-type polarization to occur at the surface of the measuring
electrode (Morrow and b o p , 1975). T h i s requires careful cleaning be-
tween titrations. Morrow and Roop (1975) recomnended the addition of
bromide to the cell and adjustment of electrode potential to permit
free chlorine to be measured without significant interference. Sengupta
et al. (1978) found negligible interference from 1 0 3 - , S 2 0 8 2 - , and Fe(1II)
- -
at 1 mg/L, but when iodide was added, H 2 0 2 , Rr03 , and C 1 0 3 gave non-
quantitative, but measurable, responses.

Phenylarsineoxide solution is very stable, and amperometric titra-

tions are relatively unaffected by color, temperature, and turbidity
(Opresko, 1980) .
The accuracy and precision of the amperometric titration method as
developed by Brooks and Seegert (1.979) compared favorably with that re-
ported by Lishka and McFarren (1971). For example, for a solution con-
taining free chlorine a t 0.695 mg/L, Brooks and Seegert (1979) found a
relative error of -10.8% and a relative standard deviation of 1.1%.
Because of consistently low results, they questioned the use of the
iodometric method as the standard for comparison. Helz (1980) reported
a detection limit of 1.5 ug/L in natural estuarine waters. Tnis is about
an order of magnitude I.ower than the detection limit of commercial
titrators. Payne (1979) determined that the lower limits of detection
by amperometric titration were 5 to 10 krg/Z, as chlorine, He calculated
relative errors of -4 to -16% for free-chlorine residuals of 1.92 to 0 . 4 2
mg/L,with relative standard deviation of 2.5 to 12%. Nicol-son (1965)
reported the lower liiiiit: of detection by amperometric titration to be
12 u g / L .
Rice et al. (1980) conducted a comparative study of the accuracy
and precision of amperometric tit:rat:ion at several. power plant locations
with different operators and made the following conclusionis: (I) the
"ASTM D1253 Method C, back titration, would not work as written;"
 69

(2) for the concentration range 0.0 to 0.2 mg/L chlorine, the average
overall precision (standard deviation) was 3 3 p g / L for free chlorine
and 28 pg/L for total chlorine using ASTM D1253 Method A , forward
titration; and ( 3 ) for the range 0.0 to 0.2 mg/L chloririe, the average
single operator standard deviation was 12 pg/L for both free and total
available chlorine. Rice and coworkers conclude from their study using
operators familiar with approved amperometric methods arid possessing a
level of skills representative of industry practice for monitoring
chlorine in power plant discharges (river, l a k e , estuarine, and ocean
water sources) that the use of 20 pg/L total chlorine. as a minimum ef-
fluent concentration is inappropriate for plant control, compliance
monitoring, and enforcement purposes.

For analytical methodology details refer to Standard Methods (1975)

and American Society f o r Test7:ny and MuteriaZs (1976). The iodometric
method with amperometric or starch-iodine endpoint detection has been
approved by EPA for analysis of chlorine in water solutions (Federal
R e g i s t e r , 1976).

3-7.3 Ferrous-orthotolidine titrimetric method

Palin ( 1 9 5 4 ) developed the ferrous-orthotolidine method for deter-

mining free chlorine, monochloramine, dichloramine, and nitrogen tlri-
chloride. Free chlorine is determined by mixing sample, phosphate buffer
(pH 7 ) and orthotolidine, and titrating with ferrous ammonium sulfate
(FAS) solution until the blue color disappears. Addition of potassium
iodide solution and retitration until the blue color again disappears
determines the monochloramine present. Errors may be introduced by the
fading of colors but are minimized by rapid titration and a temperature
of near O°C. Dichloramine is determined by adjusting the pH to acidic
values (Q2) and titrating with FAS.

Nitrogen trichloride is determined by either extraction of a portion

of the original sample with carbon tetrachloride and titrating the aqueous
layer for HOC1 and OCl- using F A S , or destroying the H O C 1 and OCl- by re-
action with oxalic acid and titrating the relatively unreactive nitrogen
trichloride with FAS .
 70

Ni-colson (1965) r e p o r t e d t h e lower l i m i t of d e t e c t i o n o f t h e f e r r o u s -

o r t h o t o l i d i n e method was 43 Ug/T,.

3.7.4 Ferrous-DPD
...... t iI__-.I_
t r i m e t r i c method

The t i t r a t i o n o f satnples w i t h a f e r r o u s ammonium SUI-fate s o l u t i o n

u s i n g N,N-diethyl-p-phenylenediamine (DPR) as a n i n d i c a t o r w a s developed
by P a l i n (1957). Presumably t h e t t t r i m e t r i c t e c h n i q u e overcomes t h e prob-
l e m s a s s o c i a t e d w i t h t h e DPD i n s t a b i l i t y t h a t i m p a i r t h e u s e o f t h i s com-
pound i n c o l o r i m e t r y (Johnson, 1978; Sengupta e t a l . , 1 9 7 8 ) . Titration
of r e p l i c a t e s a m p l e s w i t h and w i t h o u t K I and a t t l i - f f e r e n t pB v a l u e s pro-
v i d e s a b a s i s f o r d i s t i n g u i s h i n g t h e v a r i - o u s o x i d a n t s i n t h e samples.

Marks e t a l . (1951) s t u d i e d the DPD t i t r a t i o n method. They d e t e r m i n e d

t h a t f o r IIOCl, t h e method i s a c c u r a t e and r e l i a b l e , A t lower t e m p e r a t u r e s
f o r t h e d e t e r m i n a t i o n of monochloramine, t h e p r e c i s i o n an3 r e l i a b i l i t y o f
t h e DPD method i s s a t i s f a c t o r y . However, a t h i g h e r t e m p e r a t u r e s , the
method i s u n s a t i s f a c t o r y . T h e method g i v e s e r r a t i c r e s u l t s f o r d i c h l o r -
amine a t l o w t e m p e r a t u r e s and i s u n s a t i s f a c t o r y at t e m p e r a t u r e s n e a r 25OC.

N i c o l s o n (1965) r e p o r t e d the lower l i m i t of d e t e c t i o n f o r t h i s method

t o b e 11. ~ i g / L .

F o r a n a l - y t i c a l methodology deti3i.l.s r e f e r t o Standard Methods (1975).

The ferrous-DPD t i t r i m e t r i c method has b e e n approved by EPA f o r a n a l y s i s
of c h l o r i n e i n water s o l - u t i o n s ( F e d e n f l Register, 1 9 7 6 ) .

3.8 Comparative S t u d i e s

3.8. I Nicolson S t u d 1

Nico3.son (1.965) e v a l u a t e d n i n e c o l o r i m e t r i c and t h r e e t i t r i m e t r i c

methods used a t t h a t t i m e f o r d e t e r m i n i n g f r e e c h l o r i n e i n water. Cri-
t e r i a used f o r comparing t h e methods were s t a b i l i t y of c o l o r e d r e a c t i o n
products, p r e c i s i o n O F a n a l y s i s , accuracy, s e n s i t i v i t y , s p e c i f i c i t y ,
l i n e a r i t y of t h e c a l i b r a t i o n c u r v e , e f Ecct of t e m p e r a t u r e , s t a b i l i t y of
r e a g e n t s , and s i m p l i c i t y of the method.

I n t h e a b s e n c e of combined clil ox-i-nc? (monochl orarnine) , N i c o l s o n (196.5)

d e t e r m i n e d t h a t t h e cyanogen c h l o r i d e - b a r b i t u r i c a c i d method w a s t h e b e s t
 71

of the methods evaluated for determining free chlorine. In the presence

of monochloramine, the DPD-colorimetric method was more satisfactory.
Nicolson did not evaluate the methyl orange method because of nonlinear
calibration curves. Nicolson found the titrimetric methods were less
reproducible than the spectrophotometric methods.

The precision and limit of detection as determined by Nicolson (1965)

for several methods are listed in Table 5.

3.8.2 Analytical Reference Service Water Chlorine (Residual) N o . 1

--I__--

The Analytical Reference Service of the Consumer Protection and

Environmental Health Service conducted an evaluation of nine methods for
determining free and total chlorine (Lishka et al., 1 9 6 9 ) . Seventy-two
participating laboratories analyzed three samples that when prepared
properly were to contain the following: sample one, 0 . 8 3 mg/L free
chlorine and 1.0 mg/L combined chlorine; sample two, 0.80 mg/T, free
chlorine; and sample three, 0.64 mg/L combined chlorine. The samples
were analyzed by two referee laboratories using the amperometric titration
method, and the values obtained agreed well with results obtained by a
third referee laboratory using SNORT, ferrous-DPD, and iodometric methods.
Statistical data are available in Lishka et al. (1969). They concluded
the following: "The best overall accuracy and precision was shown by the
ferrous-DPD method, followed closely by the methyl orange, SNORT, and
amperometric methods. The leuco crystal violet method produced poor
results €or sample 1 but was quite acceptable for samples 2 and 3.
...The lack of accuracy of the orthotolidine and orthotolidine-arsenite
methods make them least acceptable, although all methods (with the possible
exception of ferrous-DPD) appear to have comparable precision."

S o l l o et al. (1970) state the data gathered by Lishka et al. (1969)

do not justify the conclusions reached. S o l l o and coworkers contend
there is not enough evidence to support any "rating" of the nine methods:
"Each method evaluated for the determination of chlorine when used-I_-

properly and according to specified instructions can be quite acceptable"

l__ll_

Sollo et al., 1 9 7 0 ) . In their critical review they state that 16 of the

72 participating laboratories reported results that deviated from those
 Table 5. Precision and limit of detection of analytical
methods for determining free chlorine
(Nicolson, 1 9 6 5 )
...._..._.l.
~l..
.. ...............
Precision, ‘2 __I_._.I._ Limit
Chlorine Chlorine of detection
(0.1 mg/L) (0.5 mg/L) (ug /TA

Cyanogen ehloride-
barbituric a c i d 3.48 1.85 0.47

DPD-colorimetric 4.04 1.95 3.6

Acid-orthotolidine 4.14 3.01 1.4

Aiip ex o me t r i c t i.tra t ion 7.28 3.94 12

Ferrous-DPD-ti. trimetric 7.20 4.53 11

Ferrous-or tho tolidine

t i t )r iine t r i e l.h.40 2.76 43
 73

of t h e r e f e r e n c e l a b o r a t o r i e s by o n l y 0.08 t o 0.15 mg/L on a l l methods

tested. The a v e r a g e relative d e v i a t i o n f o r t h e s e 1 6 l a b o r a t o r i e s w a s
<20%. S o l l o e t a l . c o n t e n d t h a t t h e u s e of t h e v a l u e s d e t e r m i n e d by
t h e s e c o n s i s t e n t l y competent l a b o r a t o r i e s i s more o b j e c t i v e t h a n u s i n g
t h e v a l u e s d e t e r m i n e d by a l l t h e l a b o r a t o r i e s . For example, 1 2
l a b o r a t o r i e s c o n s i s t e n t l y had r e l a t i v e d e v i a t i o n s > 5 0 % , and i n c l u s i o n
o f t h e r e s u l t s from t h e s e l a b o r a t o r i e s i n t h e s t a t i s t i c a l a n a l y s i s
b i a s e d t h e r e s u l t s toward p o o r e r p r e c i s i o n and a c c u r a c y . Thus S o l l o
and coworkers b e l i e v e t h e methods s h o u l d b e r a t e d by c o n s i s t e n t l y compe-
tent laboratories. T a b l e 6 shows t h e d a t a r e c a l c u l a t e d by S o l l o e t a l .
(1970) u s i n g t h i s c r i t e r i o n .

S o l l o e t a l . (1970) c o n c l u d e t h e f o l l o w i n g : "It i s clear t h a t t h e

methods are s a t i s f a c t o r y , and t h e f a i l u r e s l i e w i t h a s t o n i s h i n g l y poor
l a b o r a t o r y p e r f o r m a n c e , which h a s n o t h i n g t o do w i t h t h e p r e s c r i b e d
methodology. 'I

3.8.3 A n a l y t i c a l _ R e f e r e n c e Service Water C h l o r i n e ( R e s i d u a l ) N o . 2

I t w a s concluded from t h e p r e v i o u s s t u d y ( L i s h k a e t a l . , 1969) t h a t

t h e p r e c i s i o n of a l l methods e v a l u a t e d w a s p o o r e r t h a n a n t i c i p a t e d b e c a u s e
of t h e v a r i a b i l i t y i n s a m p l e p r e p a r a t i o n from d r y m i x t u r e s , Therefore,
t h e A n a l y t i c a l R e f e r e n c e S e r v i c e of t h e Environmental P r o t e c t i o n Agency
conducted a s u b s e q u e n t e v a l u a t i o n of a n a l y t i c a l methods f o r which t h e
c h l o r i n e - c o n t a i n i n g s a m p l e s w e r e p r e p a r e d from s t r o n g c h l o r i n e s o l u t i o n s
s e a l e d i n g l a s s ampoules s t o r e d i n t h e d a r k . Seventy-one l a b o r a t o r i e s
p a r t i c i p a t e d i n t h e s t u d y by a n a l y z i n g t h r e e s a m p l e s : s a m p l e I, 0.44 mg/L
f r e e c h l o r i n e ; sample 2, 0.98 mg/L f r e e c h l o r i n e ; sample 3 , 0.05 mg/L f r e e
c h l o r i n e and 0.66 mg/L t o t a l c h l o r i n e . S t o c k s o l u t i o n s were s t a n d a r d i z e d
by i o d o m e t r i c t i t r a t i o n , and t h e d i l u t e d s a m p l e s w e r e checked ampero-
m e t r i c a l l y by EPA s t a f f and a r e f e r e e l a b o r a t o r y ( L i s h k a and McFarren,
1971).

L i s h k a and McFarren (1971) concluded from t h i s s t u d y t h a t t h e b e s t

a c c u r a c y and p r e c i s i o n w a s o b t a i n e d b y t h e l e u c o c r y s t a l v i o l e t and SNORT
p r o c e d u r e s , f o l l o w e d by t h e D P D - t i t r i m e t r i c , amperometric t i t r a t i o n , DPD-
c o l o r i m e t r i c , and m e t h y l o r a n g e p r o c e d u r e s . The p o o r e s t p r o c e d u r e was
 Table 6. Analysis of Analytical Reference Service Water C h l o r i n e
(Residual) No. 1 ( S o l l o et al., 1970)

Sixteen selected
laboratories All laboratories
Average Average
deviation Number of deviation Number of
Method (.lg/L 1 laboratories (rr,giLj laboratories

SNORT 0.062 4 0.126

Ferrous-OT 0.080 3 0.330 19

Ferrous-DPD 0.083 6 0.178 19

Azperometric 0.095 8 0.213 24

Iodometric 0.120 7 0.251 32

Methyl orange 0.125 6 0.27s 28

Orthotolidine 0.145 2 0.390 $7

Orthotolidine-arsenite 0.167 5 0.480 23

Leuco crystal violet 0.213 5 0.313 18

 75

the orthotolidine-arsenite. However, the relative mean error of the

leuco crystal violet method is low compared to the other methods because
of the small number of laboratories doing the analysis. Selected data
from the Lishka and McFarren (1971) study are presented in Tables 7 and 8 .
The data reported by the individual laboratories show considerable vari-
ation in determined values thus indicating that laboratory experience
and competency may play a significant role in the relatively poor pre-
cision and accuracy found f o r the methods in this comparative study.

3.8.4 Bender Study

Bender (1978) evaluated eight methods for determining total

chlorine - all based on the iodide-iodine reaction using four sample
matrices (drinking water, river water, secondary effluent from a waste-
water treatment plant, and untreated wastewater). Seven replicate
determinations were used to determine the precision of the methods.
Accuracy was determined in terms of percent yield as compared with the
iodometric (starch endpoint) method, Bender (1978) concluded that each
of the methods worked well in certain matrices,but not in others. He
concluded that comparison should be made of each method with the iodo-
metric titration (arnperometric or starch-iodine endpoint), DPD-colorimetric,
o r DPD-titrimetric method as recommended in the Federal Register (1976)
to ensure the method is compatible with the sample matrix. Tables 9 to
11 present the precision and accuracy of the methods as determined for
drinking water, river water, and secondary effluents.

3.8.5 Comparative studies of amperometric techniques

Seaman et al. (1980) have compared three on-line monitoring instru-

ments for measuring the chlorine residual with the amperometric titrator.
The on-line monitoring instruments were a total residual chlorine-membrane
electrode (polarographic-membrane electrode), the iodometric method for
total chlorine using a specific ion electrode f o r iodine, and an
amperometric-type analytical instrument. Factors of concern in the
study Were accuracy, precision, sensitivity to changes in feed rate,
time-of-day behavior, minimum detectability, and baseline drift. The
 76
a\ r-
N 0
f I
P
0
d
k
3
L)
b)
4 \2) rl
0 In
I I
I-. vl
Q rl
m
rl u-l
0 rl
c7 0
Q 0
r-l m
N 4
c7
u-l N
rl -3‘
m Q
0 8
u
a,
rl
0
v-4
3
 77

Table 8. Compari.son of analytical methods for determining

total chlorine in aqueous solution containing 0.66 mg/L
total chlorine (Lishka and McFarren, 1981)

Precision
Relative Accuracy,
Standard standard re 1at ive
deviation deviation mean error
Method (w/L 1 (%I (X)

Methyl orange 0.143 21.7 +4.4

Leuco crystal violet 0.089 13.5 -1.1

SNORT 0.110 16.7 -4.8

Ferrous-DPD titrimetric 0.121 18.3 -4.7

DPD-colorimetric 0.210 31.8 +15.6

Amper ome t r ic 0.171 25.9 -16.4

Orthotolidine-arsenite 0.218 33.0 -13.9

 78
CJ
m
a
4
\c,
CJ
m
0
8
b
a
0
.j-
cn
6
u
-4
k
u
a,
k
 79
h
CI
(d
k I
p. 03 0 cn 0
3 0
I
z m
V h rl
0 0 N 03 03
r-i 0 N h r-..
4 rl rl
z
h h 0 e al rl m
b\ N m m rl h m
rl
m cu N a
0 0 hl h hl
0 0 0 0
0 0
0 0 0 0 0 0
0 e
m 00
h
rn a
03 W rx N
# m p.
0 0 0 0 0 0 0
cg Lo W
I 0 0
h v) W CJ
d m
I p. al
0 0 0 0 0
n
k
0
U

i
c *A
0
*rl V
u -rl
a k
u
k x
0
?I
v
.rl
U
vi
c)
ti
.rl
d
3
4-r
N k
2
U 0
d
0 *rl
0 k
l 0
4
PI ?c
F3 W
 w
0
-d Q.
fo 0
Y
0 %
rt
%ci Y
P*
Y 0
P"
n

? I
Ln I
0

? r
c P
l-J I-'
a

a m
0 P
0 0
w m
d
i
D
3
^I.

J.
n
3
3

m w
m a
P. Y c
0 o m
3;

co I
10
I
0

08
 81

total residual chlorine-membrane electrode was found to be reliable,

accurate, and precise in the field. The investigators determined that
there was no statistically significant difference between the total
chlorine-membrane electrode and the amperometric titration. They did
note, however, that significant differences did exist between both the
iodometric method with specific ion electrode and the amperometric-type
analytical instrument when compared with the amperometric titration.

Four chlorine monitoring techniques were evaluated by Sugam et al.

(1981): manual amperumetric titration, automatic amperometric
titration, amperometric back titration, and chlorine-flux monitor. The
instruments were tested under field operating conditions, with field
operators having no previous experience with the methods. Three field
locations were used: (1) a freshwater site, (2) a brackish-water site,
and ( 3 ) a seawater site. The study focused on analysis of the total
residual oxidant. However, free residual "chlorine" was found to be a
significant part of the total oxidant at the freshwater and seawater
sites and was present in only trace amounts at the brackish-water site.

Sugam et al. (1981) found no inrerference at any o f the

locations that was attributable to natural oxidant background. They
found the back tlitration method yielded slightly less oxidant than the
forward titration in seawater. They recommended the use o f either the
manual o r automatic forward amperometric titration for utility appli-
cations. They determined that either can be used with acceptable
accuracy and precision down t o concentrations of 0.036 (manual) and
0.021 (automatic) mg/L chlorine. Over a range extending to at least
1.0 mg/L chlorine, relative precision (95% confidence level) was +20%,
-17% for the manual method, and +30%, -23% for the automatic methods.
The chlorine-flux monitor cannot be used at levels below 0.021 mg/L
chlorine, but Sugam arid coworkers did question its reliability for
analyses in brackish water and seawater.

3.8.4 Comparative study on chlorinated se-awater

In .January 1980, an ASTM Intercomparison Workshop was held at

Kosenstiel School of Marine and Atmospheric Science, University of
Miami, as described in ASTM Report No. RR:D19-1867 (Marinenko, 1980).
 82

S i x d i f f e r e n t o p e r a t o r s p a r t i c i - p a t e d i n t h e workshop, r e p r e s e n t i n g
f i v e d i f f e r e n t methods d e s i g n e d as f o l l o w s :
A - PA0 ( p h e n y l a r s i n e o x i d e ) back t i t r a t i o n u s i n g s p e c t r o -
photometric endpoint
B - Chi-orine E l e c t r o d e
C - C h l o r i n e Flux-Monitor
D - C h l o r i n e Flux-Monitor
E - hmperometric Forward T i t r a t i o n
P - P o l a r o g r a p h i c El.ectrode

ln T a b l e 1 2 , t h e I i r s t coluinn d e s i g i i a t e s c h l o r i n e s o l u t i o n numbers
2-5. The i n i t i a l c h l o r i n e demand i n Gulf S t r e a m w a t e r was s a t i s f i e d by
c h l o r i n a t i o n and t h c r e s u l t i n g w a t e r of r e l a t i v e l y low c h l o r i n e demand
w a s used f o r p r e p a r a t i o n o f known c o n c e n t r a t i o n sodium h y p o c h l o r i t e
solutions. S o l u t i o n 1 was t h e "blank" G u l f S t r e a m w a t e r used f o r p r e p a -
r a t i o n of a l l s o l u t i . o n s . As may b e seen from t h e d a t a i n Table 1 2 , t h e
r e s u l t s Erom t h e use of t h e v a r i o u s methods a r e d i s c o r d a n t t o a n e x t e n t
thaL g r e a t l y e x c e e d s t h e presunlei! a c c u r a c y and p r e c i s i o n of t h e methods.

3.9 Summary of A n a l y t i c a l Methods

The voluminous l i t e r a t u r e c o n c e r n i n g a n a l y t i c a l methodology f o r

a c t i v e c h l o r i n e - c o n t a i n i n g specFes i n aqueous media h a s been reviewed
with ~TJO major o b j e c t i v e s : (1) t o assist i n e v a l u a t i n g t o x i c i t y d a t a
r e l a t i v e t o t h e meani-ng of r e p o r t e d a n a l y t i c a l concentrali:i.c:ins o f avail-
a b l e c h l o r i n e , and ( 2 ) t o a s s i s t i n e v a l u a t i n g methodology for t h e
a n a l y s i s of low c o n c e n t r a t i o n s C J ~ chlorine or oxidant. T a b l e 1.3 surn-
marizes t h e p r i n c i p a l techniques c u r r e n t l y i n use, t h e i r a p p l i c a b i l i t y ,
and t h e lower limits of d e t e c t i o n .

Addi.iional. r e s e a r c h is needed t o deter-mine t h e l i m i t a t i o n s of t h e

several " b e s t " a n a l y t i c a l methods. With t h e ci.irrently a v a i l a b l e d a t a ,
i t i s d i f f i c u l t t.o draw c o n c l u s i o n s r e g a r d i n g s e l e c t i o n of a n a n a l y t i c a l
method m o s t s u i t a b l e Tor a n a l y s i s of t h e w a t e r saii1pl.e b e i n g a n a l y z e d I

A review of t h e c o m p a r a t i v e s t u d i e s o f e x i s t : i n g methods i n d i c a t e s t h e
need f o r a comprehensive e v a l u a t i o n of the methods i n several sample
,

a
Table 12. Chlorine concentration in seawater (measured by
six different experimentalists and five different methods)

Nomina1
Solution concentration
No. of c1 A B C D E F

2 0.011 0.019 0.065 0.016 0.009 0.012 0.013

2 0.090 0.072 0.100 0.050 0.032 0.074 0.045

4 0.451 0.409 0.372 0,282 0.228 0.317 0.306 03

w

5 4.508 4.414 5.90 3.514 3.352 3.072 3.79

aThe values in the table were corrected for decay.
 T a b l e 13. S u m a r y of a p p l i c a b i l i t y of a n a l y t i c a l methods f o r e v a i l a b l e c h l o r i n e
( f r e e and combined o x i d a n t s p e c i e s ) . For d e f i n i t i o n o f lower l i m i t s
O E d e t e c t i o n , see s e c t . 3 . 1 . 1 .

Approximate Lower l i m i t
of detection
(ug/L as c l )
For Triore Natural
d e t a i l s see Laboratory water A v a i l a b l e c h l o r i n e ( o x i d a n t species)
Method below s e c t i o n standards sample Total Free Combined NH2C1 NHCl2 NC13

Po t e r,tlime t r y 5.2 5 0 a , 3' X

Anp e r ome 5, r y 5.3 2a 21C X

d
Spectrophotometry 5.4 0.5 X X

Colorimetry 5.5
Acid-orthotolidine 5.5.1.1 1.4e x X
OTk 5.5.1.2 X x X
f
SIJGRT 5.5.1.3 2.1- x X x X X
DPD-colorimetric 5.5.2 L e , 9,5', 16" X X x x x X
LCV 5.5.3 5" X X X
Methyl orang2 5.5.4 X X X
FACTS 5.5.5 3 . 1 g , 12' x X X
Cyanogen c h l o r i d e -
barbituric acid 5.5.6 0.5e X

Chemiluminescence 5.6 3ai X

Titriinetry 5.7 h
Iodometric 5.7.1 4 0 e , 0 . 5-$50d X
Amp er one t r i c 5.7.2 1 2 , 5-10 1.5', 21-36' X X X
Perrous-orchotolidjne 5.7.3 43e X X X X x x
Ferrous-D?D- titrime t r l c 5.7.4 11e X X X x x X

aSengupta e t a l . ( 1 9 7 8 ) . ZJ. D. .?ohnson, p e r s o n a l coiiufimication (1981).

'Xigcion e t a ~ .(197s). .Standard h'ethods ( 1 9 7 5 j .
e
d C o m e r c i a l equipment, Suga.11 e t a l . ( 1 9 8 ~ ) ~
2 Isacsson e t al. (1978)-

C a r p e n t e r (19651. iModiFied equipment, X e l z ( 1 9 8 0 ) .

e
fNiroison (1965). Payne ( 1 9 7 9 ) ,
' Johnsor: and Overby ( 1 9 6 9 ) .
 85

matrices including seawater. This evaluation should include, besides

accuracy and precision, a determination of the limit of detection using
(to the extent possible) a standard frame o f reference. Research should
continue on the analysis of chlorine and chlorine-produced oxidants at
the parts-per-billion concentration and lower.

3.9.1 Selection of method

For analysis of chlorine in water solution, the EPA recommends the

iodometric titration (amperometric or starch-iodine endpoint), DPD-
colorimetric or the DPD-titrimetric methods (Federal R e g i s t e r , 1976).
Bender (1978) suggested that methods selected for analysis of oxidants
in a particular sample matrix should be compared with these EPA recom-
mended methods to ensure the selected method is compatible with the sample
matrix. The following discussion concerning the selection of methods re-
lates principally to sample matrix and does not deal with the analysis of
trace or parts-per-billion concentrations.

Natural and treated waters. For natural and treated waters the ampero-
metric titration method is accepted a s a standard of comparison for free
and combined chlorine. It is minimally affected by turbidity, c o l o r ,
temperature variations, and common oxidizing agents. The iodometric
method (forward or back-titration) with starch-iodine endpoint detection
is suitable for chlorine concentrations greater than I mg/L. The Eerrous-
DPD-titrimetric method is suitable for free chlorine determinations and
for mixtures of free and combined chlorine. Free chlorine may be deter-
mined by the SNORT and DPD-colorimetric, but increasing concentrations of
monochloramine may produce increasing interference with this determination.
Combined fractions may be estimated using SNORT and DPD-colorimetric. Free
chlorine, total chlorine, and combined chlorine may be determined by the
LLCV method with minimal monochloramine interference in the free chlorine
determination. Oxidized manganese interferes with SNORT, DPD-colorimetric,
and LCV determinations. Dichloramine ( 0 to 9 mg/L as chlorine) does not
affect free chlorine determinations by amperometric, SNORT, DPD, or LCV
methods. However, nitrogen trichloride reacts partially as free chlorine
in all except the LCV method. The FACTS method was developed specifically
 86

f o r f r e e c h l o r i n e and i s u n a f f e c t e d by s i g n i f i c a n t c o n c e n t r a t i o n s of com-
b i n e d c h l o r i n e and o x i d i z e d manganese. All c o l o r i m e t r i c p r o c e d u r e s are
s u b j e c t t o i n t e r f e r e n c e s by sample c o l o r and t u r b i d i t y (Standard Methods,
1975).

P o l l u t e d waters. I n p o l l u t e d waters, chi-orine w i l l e x i s t p r i n c i p a l l y

i.ra the combined s t a t e as c h l o r a m i n e s and o r g a n i c c h l o r a m i n e s . A t t h e same
time u n s a t i s f i . e d c h l o r i n e demarid may e x i s t s u c h t h a t a d d i t i o n of r e a g e n t s
f o r c h l o r i n e deterrn:i.nation may p e r m i t loss of c h l o r i n e t h r o u g h c o n t i n u e d
r e a c t i o n w i t h t h e c h l o r i n e demand. Thus i n wastewater t h e d i f f e r e n t : i . a t ion
between f r e e and combined c h l o r i n e i s n o t o r d i n a r i l y made. Standard Methods
(1975) recommends t h e amperometric t i t r a t i o n method f o r d e t e r m i n i n g free
clilmrine i n wastewater b e c a u s e i t i s n o t s u b j e c t t o i n t e r f e r e n c e s from
c o l o r , t u r b i d i t y , i r o n , mangan.ese, o r n i t r i t e . The SNORT and DPD methods
r e q u i r e a d d i t i o n of a r s e n i t e immediately a f t e r r e a g e n t addi-Lion t o avoi.d
i n t e r f e r e n c e by monochloramine. The LCV method i s less a f f e c t e d by mono-
chloramine and a r s e n i t e addi:t:i.on m i n i m i z e s this e f f e c t e However ~ the
combination monochloramine and n i t r i t e s e r i o u s l y i n t e r f e r e s w i t h f r e e
chl.ori tie deter1ii.i.nation.s u s i n g the LCV met:hod. The FACTS f r e e c h l o r i n e
d e t e i m i n a t i o n i s u n a f f e c t e d by combined c h l o r i n e , n i t r i t e , i r o n , and
m a n g a n e ~ e (Standard MeLhods, 1 9 7 5 ) .

Standard Methods (1975) recommends tlir i o d o m e t r i c back t i t r a t i o n

method w i t h e i t h e r t h e amperometric o r s t a i - c h - i o d i n e e n d p o i n t d e t e c t j O[I

f o r d e t e r m i n i n g t o t a l c h l o r i n e i n t h e p r e s e n c e of s i g n i f i c a n t c o n c e n t r a t i o n s
of o r g a n i c matler. The amperornctric e n d p o i n t i s i n h e r e n t l y more a c c u r a t e
and n o t a f f e c t e d by c o l o r and t u r b i d i t y a l t h o u g h some m e t - a k may i n t e r f e r e .
Color and t u r b i d i t y i n t h e sample may c a u s e d i f f i c u l t y w i t h t h e s t a r c h -
iodine endpoint. SNOKT, DPD-titrimetric a n d c o l o r i m e t r i c , and LCV ruelhods
a r e a p p l i c a b l e t o t h e d e t e r m i n a t i o n of t o t a l c h l o r i n e i n p o l l u t e d s a m p 1 e . s .

Seawater. The a n a l y s i s of o x i d a n t s p e c i e s i n c h l o r i n a t e d seawater

is R subject of c - u r r e n t l y a c t i v e r e s e a r c h . The methods c u r r e n t l y u s e d are
s p e c t r o p h o t o m e t r y , p o t e n t i o m e t r y , amperometry, and amperometric t i t r a t i o n
(Table 1 2 ) De:Ei.nitive c o n c l u s i o n s have n o t been made r e g a r d i n g recommended
procedures.
 87

Sengupta et al. (1978) compared DPD-colorimetric oxidant determi-

nations in freshwater and artificial seawater. They found there was
either a large chlorine demand by the seawater or that the apparent sensi-
tivity of the DPI) method was reduced significantly, They attributed the
effect to the high chlorine demand of the seawater. They concluded that
the method was feasible for determination of chlorine-produced oxidant i n
seawater if the amount of other oxidizing i o n s are present only in trace
amounts.

Sengupta et al. (1978) determined that bromamine samples reacted with

syringaldazine t o produce an orange color. They concluded that the for-
mation o f bromamines in chlorinated seawater would decrease the sensitivity
of the FACTS colorimetric method for oxidant determinations in seawater
as compared with freshwater.

3.9.2 Analytical measurements/toxicity data

Judgments concerning reported concentrations of chlorine or oxidant

concentrations in toxicity studies must be made for each individual s t u d y
based on the following criteria.
I. Water q u a l i t y . Determinations made on high-quality water, free from
pollution and ammonia, may be Interpreted with a higher degree of
confidence than those made on highly polluted waters. Most published
procedures perform w e l l in relatively clean systems free from inter-
ferences (Sorber et al., 1977). Values reported on highly polluted
waters ( e . g . , wastewater effluents) may be low, as discussed in
Standard Methods (1975). Conclusions regarding the effect of water
quality on analytical data are best made by the researcher reporting
the data.
2. Analyst eceyertiso. Analytical results are highly dependent on the
level of expertise and knowledge of the analyst.
3. Mzthudulogp. Analytical methodology must be reported to permit: data
evaluation.
4. S t a t i s t i c a l significance. Statistical. treatment of data and reports
on significance facilitate evaluation o f reported concentrations.
This includes replicate analyses and rigorous quality assurance/
quality control procedures.
 88

3.9.3 A n a l y s i s of low c o n c e n t r a t i o n s

Accurate and p r e c i s e a n a l y s i s o f c h l o r i - n e and c h l o r i n e - p r o d u c e d

o x i d a n t s p e c i e s i s h i g h l y depeiiileriL: upon t h e s k i l l and e x p e r t i s e of t h e
andyst:. T h i s i s e s p e c i a l l y t r u e f o r a n a l y s i s of o x i d a n t c o n c e n t r a t i o n s
i n t h e par-er-billion range. The a n a l y s t must b e c o g n i z a n t of t h e
l i m i t a t i o n s of t h e a n a l . y t i c a 1 method and t h e p o s s i b l e ii1tel:feriilg sub-
s t a n c e s i n t h e water sample. Although a c c u r a t e and p r e c i s e a n a l y s e s a t
t h e p a r t s - p e p b i l l i . o n l e v e l may n o t c u r r e n t l y be nchievabl-e w i t h commercial
a n a l y t i c a l equipment and o p e r a t o r s p o s s e s s i n g t h e l e v e l of s k i - l l s r e p r e -
s e n t a t i v e of t h e i n d u s t r y p r a c t i c e For m o n i t o r i n g c h l o r i n e i n power plant
discharge:; ( R i c e el: a].. , 1980) , a n a l y s e s a t tl-rat parts-per-’oi.’l.bion level.
are a c h i e v a b l e by h i g h l y competent c h e m i s t s w i t h m o d i f i e d a n a l y t i c a l
i.nstriiiiients (Helz, 1980).
Sengupta e t a l . (1978) conclude t h a t o p t i c a l methods ( c o l . o r i m e t r i c )
w i l l n o t b e a b l e t o p r o v i d e r e l i a b l e d a t a f o r a n a l y s i s of c h l o r i n e o r
ox?’.dant r e s i d u a l s a t p a r t s - p e r - b i l l i o n l e v e l s i n n a t u r a l waters. They b a s e
t h i s concl-usion on an e v a l u a t i.on of most a c c u r a t e and p r e c i s e a n a l y t i c a l
m e t h o d o l o g i e s c u r r e n t l y i.n u s e and on i n t e r f e r e n c e s p r e s e n t i n n a t u r a l
waters. Most s c i e n t i s t s concerned w i t h a n a l y s e s a t t h e p a r t s - p e r - b i l l . i . o n
l e v e l now recommend e l e c t r o c h e m i c a l t e c h n i q u e s p r i n c i p a l l y ainperome tri.c
t e c h n i q u e s u s i n g a n a l y s t s w i t h a hi-gh degree o f e x p e r t i s e .
O t h e r t e c h n i q u e s are b e i n g d e v e l o p e d and may p r o v e e q u a l l y r e l i a b l e
i n t h e f i s ~ u r e . The c h o i c e of method and t h e s i g n i f i c a n c e o f t h e d a t a
g e n e r a t e d by t h e method a r e a f u n c ~ i o no f t h e n a t u r e and q u a l i t y of t h e
water b e i n g a n a l y z e d e I n c r e a s e d knowledge c o n c e r n i n g t h e c h e m i s t r y of
s y s t e m a t i c e r r o r s (Helz, 1980) and i n t e r f e r e n c e s i s needed b e f o r e u l t r a -
low-.level a n a l y s e s can become r o u t i n e .
 89

4. ENVIRONMENTAL FATE

Relatively little information exists concerning the environmental

fate, transport, and distribution of chlorine and chlorination products
in natural waters receiving chlorinated discharges such as cooling waters,
process waters, and wastewaters. The chemistry and interrelationship of
free oxidant (HOC1, OC1-, HOBr , OBr-) , combined oxidant (chloramines,
organic chloramines, bromamines, organic bromamines, mixed halamines),
and reaction products (chloro- and bromoorganics, oxid-ized o r g a n i c s ,
chlorate and bromate ion, oxidized metal ions, nitrogen, and oxygen)
are schematically shown in Fig. 4 . The chemical products and pathways
are principally controlled by reactant concentrations, pH, temperature,
salinity (including bromide concentrations), and sunlight, in addition t o
the chemical kinetics and equilibria for the many possible reactions.

The. ultimate decomposition products of free chlorine in natural

waters are chloride, oxidized organics, chloroorganics, oxygen, nitrogen,
and possibly chlorate and nitrate. Depending upon the bromide content of
the chlorinated waters, other possible products are bromate and bromo-
organics. The chlorine consumed in these reactions represent what has
been termed chlorine demand. Only a few percent of the chlorine added
t o the water are found in the many possible haloorganic products (e.g.,
trihalomethanes). A larger fraction of the added chlorine is probably
consumed in the oxidation of organics. The fractions disproportionating
to halates, decomposing to oxygen, or oxidizing metal ions and other
materials are relatively unknown. However, the decomposition of oxidant
to oxygen and halate ion is presumed to be considerably less than the
available oxidant consumed in the decomposition of chloramines and brom-
amines. Consequently, very little is known concerning the concentrations
of these products in receiving waters and their ultimate distribution and
fate. For specific details concerning chlorine chemistry and possible
chemical reactions, see Sect. 2.
 u3
0

Fig. 4 . Principal chemical pathways for reactior:, degradation,

and environmental fate of free available chlorine in the aquatic environ-
ment. Presumed pathways ( n o t yet proven) are given b y dashed arrows,
Compounds formed at different places in the reaction scheme are desig-
n a t e d with superscripts a arid b To assist in understanding interrelation-
ships. Halides (C1- and Br-) are not depicted b u t are products of many
of the chemical pathways.
 91

4.1 Freshwater System

The reactions on the right side of Fig. 4 represent the princlpal

chemical reactions of chlorine in freshwaters and wastewaters. The rela-
tive concentrations of ammonia, chlorine, and pH are the principal
parameters determining the products. If the chlorinated water contains
bromide (as in some freshwaters and estuarine waters), then the remaining
reactions may become increasingly important as the bromide concentration
increases.

According to Johnson (19781, the stability of free chlorine in

natural water is very low because it is a strong oxidizing agent (at
pH 7, E" = 1.28 v). Consequently, it rapidly oxidizes inorganlc com-
pounds and more slowly oxidizes organic compounds. In the presence of
ultraviolet light, HOC1 oxidation of water to 0 2 proceeds at a significant
rate (Johnson, 1978; Hancil and Smith, 1 9 7 1 ) . According to Johnson (19781,
Snoeyink and Marcus determined that free chlorine (HOC1, OCl-) in nitrified
secondary effluents dosed with 3.1 mg/L chlorine and subjected to prevail-
ing sunlight and wind gave first-order decay rates of 2.1 to 7 . 4 h-l, with
half-lives of 8 t o 28 min. For similar chlorinated effluents kept in the
laboratory, without stirring and ultraviolet light (sunlight) present in
the outdoor samples, a tenfold greater persistence was measured (i.e.,
first-order decay constants of 0.19 to 0.77 h"' after an initial rapid
decay with half-lives of 10 to 30 min) with a half-life of 1 . 3 to 5 h.

Monochloramine, the principal chloramine formed in chlorinated

natural and wastewaters at neutral pH, is much more persistent in the
environment. According to Johnson (1978), Snoeyink and Marcus measured
first-order decay rate constants of 0.03 to 0.075 l'h for NH2C1 in the
laboratory and higher rate constants of 0.28 to 0.31 h-l outdoors using
chlorinated effluents. These decay rates are approximately t e n f o l d
slower than the decay of free chlorine. If discharged into receiving
waters containing bromide, NHZC1 will decompose faster probably through
the formation of N H B r C l and decomposition of the dihalamine (Trofe et al.,
1980). The rate of monochloramine disappearance is pritnarily a function
of pH and salinity. For example, at pH 7 and 25'C, the half-life of
 92

monochloramiiic i s 6 h a t 5 p p t ( p a r t s - p e r - t h o u s a n j ) s a l i n i t y and 0. /5 h
a t 35 p p t salinity; a t p H 8 . 5 and 25OC, t h e h a l f - l i f e of rnonochlor-amine
i s 188 h a t 5 p p t s a l i n i t y and 25 h a t 35 p p t s a l i n i t y . Monochloramine
woulcl be e x p e c t e d t o decompose, a l s o i n r e c e i v i n g warers v i a c h l o r i n e
t r a n s f e r t o o r g a n i c n i t r o g e n - c o n t a i n i n g compounds (Isaac and M o r r i s , 1 9 8 0 ) .

S e v e r a l i n v e s t i g a t o r s have d e v e l o p e d e q u i l i b r i u m o r e m p i r i c a l models
attempting t o p r e d i c t t h e concentration-time r e l a t i o n s h i p of t h e s e v e r a l
c h l o r i n e - c o n t a i n i n g species i n c h l o r i n a t e d f r e s h w a t e r s and w a s t e w a t e r s
( D r a l e y , 1972; Hostgaard-Jensen e t a l . , 1 9 7 7 ; Khal-anskri., 1.980; Sugam and
Welz, 1.981). H O ~ J ~ V ~eTq ,u i l i b r i u m i s p r o b a b l y n o t e s t a b l i s h e d i n t h e
chlorine-ammonia-water s y s tern. Thus equi.l.i.brium mode1.s have l i m i t e d
s i g a i f icance, E m p i r i c a l models l a c k a d a p t a b i l i t y t o changing ammonia
c o n c e n t r a t i o n s and c h l o r i n e demand cond:i.t:ions and may n o t b e v a l i d o u t s i d e
t h e c h l o r i n e d o s e r a n g e s and t i m e p e r i o d s s t u d i e d .

Consequently, L i e t z k e (L978a, 1978b) and Haag and L i e t z k e (1980)

have developed a k i n e t i c model f o r c a l c i i l a t i n g t h e c o n c e n t r a t i o n - t i m e re-
l a t i o n s h i p for t h e c h l o r i n e - c o n t a i n i n g s p e c i e s . Their model f o r fresh-
w a t e r w a s b a s e d p r i n c i p a l l y on the r e a c t i o n s l e a d i n g t o t h e p r o d u c t i o n

of t h e c h l o r a m i n e s and on an assuined c l i l ~ o r i n edemand r e a c t i o n . The mathe-

m a t i c a l f o r m u l a t i o n of t h e model i n v o l v e d t h e s o l u t i o n o f f i v e s i r n i i l t:aneous
d i f f e r e n t i a l . e q u a t i o n s r e p r e s e n t i n g k i n e t i c d a t a f o r t h e several chemical
reactions. The k i n e t i c model was v a l i d a t e d by usi.ng a c t u a l . c h l o r i n e
r e s i d u a l measurements f o r t h e c o o l i n g s y s t e m o f a n e l e c t r i c - p o w e r planL
(Lie trzke, 1978b). The p r e d i c t e d v a l u e s f o r t h e c h l o r i n e r e s i d u a l compared
f a v o r a b l y w i t h a c t u a l measured v a l u e s . 'The r e l a t i v e st-andard e r r o r f o r
t h e p r e d i c t e d v a l u e w a s 20%.

Haag ( p e r s o n a l communication, 1981) iiiudified trhe I-Iaag and L i e t z k e

k i n e t i c model t o i n c l u d e amino a c i d s I Typical r e s u l t s f o r halogen s p e c i e s
i n c h l o r i n a t e d f r e s h w a t e r a s a f u n c t i o n of t i m e r e s u l L i n g f r o m c h l o r i ~ n a t i o n
( 2 . 0 mg/L c h l o r i n e ) of a saiuple contai.ni.as 0 . 4 mg/L ammonia-nitrogen are
g i v e n i n Table 14.

RefineiiieriLs of t h e k i n e t i c model a r e needed t o p r e d j c L t h e concen-

t r a t i o n s of c h l o r o o r g a n i c s , o x i d i z e d o r g a n i c s , and i n o r g a n i c c o n s t i t u e n t s
such a s c h l o r a t e ,
 f
Y
T a b l e 14. C o n c e n t r a t i o n of a c t i v e h a l o g e n s ecies f o r
c h l o r i n a t i o n of f r e s h w a t e r (mol/L)aJ

Total
Time Chlorine chlorine
d
(min) HOC1 NH2C1 NHC12 RNHCIC NH3 RNH2 demand residual

0 2.8 10-5 o 0 0 2.9 10-5 7.1 10-6 2.1 10-5 2.8 10-5

17 3.0 x 8.9 x 2.7 x 4.8 x 2.1 x 8.6 x lo-? 8.3 x 1.4 x

38 2.4 x 6.9 x 2.0 x 3.4 x 2.4 x 8.3 x 6.3 x 1.0 x

60 2.3 x 6.7 x 1.4 x 2.4 x 2.5 x 8.0 x 6.1 x 9.0 x

aI n i t i a l c o n d i t i o n s :
pH, 7.0; t e m p e r a t u r e , 25OC; c h l o r i n e added as C 1 2 , 2.0 mg/L; c h l o r i n e demand as
'212, 1 . 5 mg/L; NH3 c o n c e n t r a t i o n as n i t r o g e n , 0.4 mg/L; RNH2 (amino a c i d ) c o n c e n t r a t i o n a s n i t r o g e n , 0 . 1 mg/L.
b P e r s o n a l communication, W. K. Haag ( 1 9 8 1 ) .
c
iV-chloroalanine, r e p r e s e n t i n g X-chloroamino acids.
dAlanine yas u s e d t o model amino a c i d s .
 94

4.2 Sali-ne Water System

I n open oceans, seawater c o n t a i n s l i t t l e ammonia, t h u s t h e p r i n c i p a l

c h e m i c a l r e a c t i o n s o f c h l o r i - n e i n seawater are t h e f o r m a t i o n of HOBr and
a s s o c i a t e d demand r e a c t i o n s ( r e a c t i o n s i n t h e c e n t e r o f Fi.g. 4 ) . In
e s t u a r i n e waters o r seawaters c o n t a i n i n g r e l a t i v e l y h i g h c o n c e n t r a t i o n s
of ammonia, t h e r e a c t i o n s r e p r e s e n t e d on t h e r i g h t and ].eft s i d e s of
F i g . 4 a l s o become i n c r e a s i n g l y i m p o r t a n t .

Johnson ( 1 9 7 7 ) f i r s t p o i n t e d o u t t h e i m p o r t a n c e of ammonia i n t h e
c h e m i s t r y of seawater c h 1 o r i n a t i . m . According t o Inman and Johnson (1978)
a t low ammonia c o n c e n t r a t i o n s i n seawater, bromamines a r e formed from t h e
hypobromous a c i d produced by t h e r e a c t i o n of f r e e c h l o r i n e ( H O C 1 , OCl-)
w i t h bromide ( p r e s e n t a t 65 mg/T, i n most s e a w a t e r ) . The d e g r e e of h a l o g e n
s u b s t i t u t i o n on t h e n i t r o g e n i s governed by t h e pH and t h e halogen-to-
ammonia r a t i o . I f t h e ammonia c o n c e n t r a t i o n i s s u f f i c i e n t l y h i g h , t h e
r a t e f o r t h e f o r m a t i o n o f moriochloramine may become c o m p e t i t i v e w i t h
bromi.de o x i d a t i o n t o hypobromous a c i d . Consequently, a m i x t u r e o f
h a l a m i n e s wi.1.1 b e produced, i n c l u d i n g N-bromo-N-chloramines ( T r o f e e t al.,
1980; Haag, 1.980).

Kongers e t a l . (1.978) d e t e r m i n e d t h a t i n t h e c h l o r i n a t i o n o f e s t u a r i . n e
waters a t 1 t o 8 p a r t s - p e r - t h o u s a n d s a l i n i t y , t h e r a t e of o x i d a n t decay
wil.1 d e c r e a s e w i t h i n c r e a s i n g ammonia c o n c e n t r a t i o n a t c o n s t a n t s a l . i n i . t y
(i.e., w i t h i n c r e a s i n g monochloramine f o r m a t i o n ) , b u t t h e r a t e of o x i d a n t
decay will i n c r e a s e w i t h inclreasi-ng s a l i n i t y ( i .e. , with i n c r e a s i n g hro-
mide c o n c e n t r a t i o n ) a t c o n s t a n t ammonia c o n c e n t r a t i o n . Helz e t a l . (1978)
d e t e r m i n e d t h a t i n t h e c h l o r i n a t i o n of e s t u a r i n e water, [;he o x i d a n t decay
w a s i n i t i a l l y v e r y r a p i d (90% decay w h i l e i n t h e c o o l i n g water system) h u t
e n t e r e d a s l o w p h a s e i n which t h e decay w a s a p p a r e n t l y f i r s t o r d e r i n
t o t a l o x i d a n t c o n c e n t r a t i o n w i t h a h a l f - l i f e of 30 t o 100 min. Other in-
v e s t i g a t o r s have al-so d e t e r m i n e d t h a t t h e o x i d a n t produced by t h e c h l o r i -
n a t i o n of seawater f i r s t d e c a y s r a p i d l y , t h e n d e c a y s at: a much s l r ~ w e s
rate. F o r example, Wong (1980) dosed seawater w i t h 5 mg/L c h l o r i n e and
d e t e c t e d r e s i d u a l o x i d a n t c o n c e n t r a t i o n s up t o 2 mg/L as c h l o r i n e a f t e r
3.5 d a y s . The compounds WORr and O B r - a p p e a r t o be t h e predominant
 95

oxidant species in these long-term studies (Wong and Davidson, 1.977).

Eppley et al. (1976) in their studies on chloriiiated seawater found an
initial rapid decline in both free and combined oxidant, followed by a
slower decline. Their observations suggested that the initial. oxidant
demand may involve organic reactions or oxidation of metal i o n s .

Experiments were conducted by Inman and Johnson (1978) to determine

the variation in halogen-containing species as a function o f chlorine-to-
ammonia ratio in chlorinated seawater. They concluded that at a 1,5 to
1.7 molar ratio of halogen to ammonia, conditions were favorable for
oxidation rather than substitution reactions and that the total oxidant
concentration decreases rapidly with time. At low ammonia concentrations
and halogen-to-ammonia ratios >3, NBr3 is the principal bromamine present.
A mixture of dibromamine and monochloramine will form when the chlorine
dose is <2.5 mg/L and the ammonia concentration is >0.5 mg/L as nitrogen
in chlorinated seawater. With Longer time and higher ammonia eoncen-
tration, NHZC1 becomes the predominant species due to more rapid broma-
mine decay. F o r relatively large chlorine doses a n d with ammonia <0./4
mg/L as nitrogen, N B r ? and HOBr are the major products.

A s long as the breakpoint for ammonia oxidation is not exceeded, the

relative rates of HOBr and NH2C1 formation are independent of the chlorine
dosage and dependent only on t h e salinity (Br- Concentration), ammonia
Concentration, and pH. Inman and Johnson (1978) concluded that at pH 8.1
and ammonia-nitrogen of 50 ug/L decreasing salinity tenfold would decrease
the rate of HOBr formation so that NH2C1 would become the predominant
halogen species. However, a decrease in pH would tend to decrease NH3
concentration and, consequently, decrease the rate of NH2C1 formation.
Large variations of ammonia and bromide concentrations are encountered
in estuarine waters.

Inman and Johnson (1978) concluded that at pH 8.1, the critical

weight ratio of ammonia nitrogen to bromide is 0.008. At higher ratios,
after 30 to 60 min, NH2Cl should be the predominant species. For lower
ratios, the major oxidant species would be d i hromamine a However, thc s m a l l
fraction of monochloramine present would persist after the bromamine
decayed.
 96

h a g and L i e t z k e (1980) d e v e l o p e d a k i n e t i c model f o r p r e d i c t i n g

hal-ogen-containing s p e c i e s i n v o l v i n g 2 1 chemical. r e a c t i o n s l e a d i n g t o t h e
f o r m a t i o n and d i s a p p e a r a n c e of t h e most i m p o r t a n t halami.ne:; and hypohalous
a c i d s l i k e l y t o be e n c o u n t e r e d i n c h l o r i n a t e d s e a w a t e r . Accurate kineti-c
d a t a e x i s t f o r f i v e of t h e chemical r e a c t i o n s . Haag and L i e t z k e e s t i m a t e d
r a t e c o n s t a n t s f o r t h e remaining r e a c t i o n s by comparisons w i t h s i m i l a r
reactions. The model r e q u i r e s the s o l v i n g of 15 s i m u l t a n e o u s d i f f e r e n t i a l
equations. T y p i c a l r e s u l t s are p r e s e n t e d i n T a b l e 15. T h i s model p r e d i c t s
t h a t bromochloramines a r e t h e predominant s p e c i e s .

The Haag and 1,iet:zke mode1 gi.ves a n e s t i m a t e of t h e t r i h a l o r n e t h a n e

p r o d u c t i o n a t low s a l i n i t i e s b a s e d on an e m p i - r i c a l r e l a t i o n d e r i v e d by
P e t e r s et: a l , (1980). The model. does n o t a d d r e s s t h e e f f e c t o f l i g h t ,
which may s i g n i f i c a n t l - y i n c r e a s e the decay rate. of h a l a m i n e s (Haag, p e r -
s o n a l communication, 1.581) -

4.3 D i s t r i b u t i o n and T r a n s p o r t

L i t t l e i n f o r m a t i o n w a s found r e g a r d i n g the d i s t r i b u t i o n and t r a n s p o r t

of c h l o r i n a t i o n p r o d u c t s i n r e c e i v i n g w a t e r s . The d i f f u s i o n o r s p r e a d of
a v a i l a b l e o x i d a n t h a s been measured by s e v e r a l i n v e s t i g a t o r s i n c o o l i n g
water d i s c h a r g e plumes [ e . g . , see Grieve e t al.. (1978)l. Principal
f a c t o r s a f f e c t i n g d i s t r i b u t i o n and t r a n s p o r t of t h e p r o d u c t s o f water
c h l o r i n a t i o n are wa1:er q u a l i t y , w a t e r f l o w ( d i l u t i o n ) , wind, s u n l i g h t
and t e m p e r a t u r e . I n p a r t i c u l a r , much of t h e a c t i v e halogen i s l o s t t o t h e
" c h l o r i n e demand" of t h e r e c e i v i n g w a t e r s . T h e t o t a l . o x i d a n t concentrat:ion
i s always considerab1.y l e s s t h a n i.f o n l y d i l u t i o n i s c o n s i d e r e d . The
chemical and p h y s i c a l p r o p e r t i e s of the c h l o r i n a t i o n p r o d u c t w i l l govern
i t s environmental f a t e . For exampl-e., t h e major e n v i r o n m e n t a l f a t e of
many low-molecular-weight c h l o r o o r g a n i c s s u c h as the trihalorriethanes w i l l
be v o L a t i . I . i z a t i o n from t h e c h l o r i n a t e d w a t e r and r e c e i v i n g waters ( J o l l e y
e t a l . , 1 9 7 8 ; Smith e t a l . ~ 1980). D i l u t i o n and r e a c t i o n of t h e o x i d a n t s
w i t h t h e r e c e i v i n g w a t e - t ' s are o f inajnr importa.nce i n r e d u c i n g a v a i l - a b l e
oxidant concentrations. The f a t e of r e s i d u a l o x i d a n t s i n r e c e i . v i n g waters
may i n c l u d e s u c h r e a c t i o n s as c h l o r a m i n e o x i d a t i o n o f bromide, h a l o g e n

t r a n s f e r t o o r g a n i c n i t r o g e n - c o n t a i n i n g compounds, and r e a c t i o n w i t h
 97
r. r. r. .t LD CD u7 W W
I I I I I I I I I
0 0 0 0 0 0 0 0 0
rl rt rl rl r-! rl rl -I rl
x X x x x x x x x
u3 3
. N 0 rt m ul m 0
0 hl hl hl N ri u3 .
l. m W
CD 03 cn (0 lc m
b
4
I
0
rl
I
0
4
I
0
rl
I
0
rl
I
0
rl
x X X x X x
m -I m ul N u3
0 rl m ul w -3 hl 0 0 0
-
N
I
0

r-4
4
0
I

0
4
I
0
u
l
I
0

r.
0
r-!
I
ri rl rl rl
X
X X X X
d
UY \o N r-i
r. 0 117
0 0 0
0 \D -3 m 4
3 f m
W W r. r. r. d d 4 .4
I
0
rl
brl
b
rl
I
0
r-
I
0
rl
I
0
r-i
I
0
r-i

I
0
r-!
0
r-
I
x X X X X x X X X
\D m r. p* rl CJ m rl c.4
0 m r-! UY m r. u3 N m hl
N
r.
r4 r-4
co d d ri r- r- r.
I I I I I I I I
0 0 0 0 0 0 0 0
rl rl rl rl rl r-! rl d
x X x x X x x x
ul rl r. 0 N .-I I-. r.
0 UY co rl m 0 ul ul m ul
0 0
r.
0 0
r^l 4 ,.* ,-4 P- r. r.
I
b
I I I I I I
o 0 0 0
rl
0
r-!
0
rl
0
rt
r-! -I r-! d
x x x w x X X x
m m ul r
l m 0-l rl N
0 m M M M 0 N r-l m N
0 N m
r. d .-* -4 r. r. r. r-
I I I I I I I I
0 0 0 0 o 0 0 0
r-!
r- r-! 4 r-! r-! r-! r-!
X x x x X x x iF
m -I m N -3 ul m m
0 r-! -3 rl rl 0 r-! rl rl rl
m ln ln 4 d d
LD m -I d 4 0 1 .-.I 7, d
I
0
r-!
b
rt
b
4
I
0
ri
I
0
r-!
I
0
Ti

I
0
r-!
l
0
rl
I
O
4
x x X x x x x x X
r-! I’- N u3 m 0 u3 N m
rl a rl N N 0 N a. 03 CD
0 rl 0 0 rl 0 0 0
a
0 0
4 m r4 m UY
 98

organic constituents. In general, the rates for such reactions will. be

lowered due to dilution.
 99

5. REFERENCES

American S o c i e t y f o r T e s t i n g Materials. 1976. S t a n d a r d T e s t Methods f o r

R e s i d u a l C h l o r i n e i n Water, p p . 292-307. I n AmuaZ Book of ASTM
--
S-bandards, P h i l a d e l p h i a , P e n n s y l v a n i a .

Bauer, K . , and C. 0. Rupe. 1971. Use of S y r i n g a l d a z i n e i n a P h o t o m e t r i c

Method f o r E s t i m a t i n g "Free" C h l o r i n e i n Water. Anal. Chem. 4 3 ( 3 ) : I-

421-425.

B e l l a r , T. A , , J . J. L i c h t e n b e r g , and R. C. Kroner. 1974. The Occurrence

of O r g a n o h a l i d e s i n C h l o r i n a t e d D r i n k i n g Water. .J. Am. Water Works
ASSOC. 66:703-706.
L

Bender, D. F. 1978. Compa~isonof Methods f o r the Determination of TobaZ

Ava<lab%e Residual Chlorine i n Various Sample Ma-brices. EPh-600/4-78-
019. U.S. Environmental P r o t e c t i o n Agency, Washington, D.C.

Black, A . P . , and G. P. Wtiitt1.e. h967a. New Methods f o r t h e C o l o r i m e t r i c

D e t e r m i n a t i o n of Halogen R e s i d u a l s , P a r t I: I o d i n e , I o d i d e , and
I o d a t e . J. h e r . Water Works Assoc, - 59:607-619.

B l a c k , A. P., and G . P. W h i t t l e . 1967b. New Methods f o r t h e C o l o r i m e t r i c

D e t e r m i n a t i o n of Halogen R e s i d u a l s , P a r t TI: F r e e and T o t a l C h l o r i n e .
J. A m e r . Water Works. Assoc. _-59:607-619.

Bongers, L . H . , T. P . O'Connor, and D. T . Burton. 1977. Bromine Chloride--

A n A l t e m u t i v e t o Chlorine fop Fouling Control in Condenser CooZ i n g
S y s t e m . EPA-600/7-77-053. U. S . Environmental P r o t e c t i o n Agency.

Bongers, .,T H., D. T. B u r t o n , L. H. Lideri, and T. P. O'Connor. 1980.

Bromine Chloride--An A l t e r n a t i v e B i o f o u l i n g C o n t r o l Agent f o r C o o l i n g
Water T r e a t m e n t , pp. 735-752. I n R. L . J o l l e y , H. Gorchev, and D. H.
Hamilton, .Jr., ( e d s . Water Ch%%inat-ion: Enuironrnentaz I v a c t and

.
Health Effeci!x, Vol. 2. Ann Arbor S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor,
Michigan

Brooks, A. S . , and G. L. S e e g e r t . 1979. Low-Level C h l o r i n e A n a l y s i s by

Amperometric T i t r a t i o n . %J. Water P o l l u t . C o n t r o l Fed. ._
51(11):2636-
2640.

B u r g e r , J. D . , and H. A . L i e b h a f s k y . 1973. Thermodynamic Data f o r Aqueous

I o d i n e S o l u t i o n s at: V a r i o u s Temperatures. Anal. Chem. -
45(3):600-602.

B u r t t s c h e l l , R. H . , A. A. Rosen, F. M. M i d d l e t o n , and M. B. E t t i n g e r .
1959. C h l o r i n e Derivatives of Phenol Causing Taste and Odor.
.J. A m e r . Water Works Assoc. 51:205-213. I
 100

C a r l s o n , R. M . , and R. C a p l e . 1978. Organochemical I m p l i c a t i o n s o f Water

C h l o r i n a t i o n , pp. 65-75. I n R. L. J o l l e y ( e a . ) Plater ChZorination:
EnvironmentaZ Impact and H z Z t h Effects, Vol. 1. Ann Arbor S c i e n c e
P u b l i s h e r s , I n c . , Ann Arbor, Michigan.

C a r p e n t e r , J. H. 1965. The Accuracy of t h e Winkler Method f o r D i s s o l v e d

Oxygen A n a l y s i s . Limnol. Oceanogr. -
10:135-140.

C a r p e n t e r , J. H . , C. A . Moore, and D. L. Macalady. 1977. E r r o r s i n

D e t e r m i n a t i o n o f R e s i d u a l O x i d a n t s i n C h l o r i n a t e d Seawater. Environ.
e .
Sci Techno1 11:992-994.
I

C a r p e n t e r , J . H , , and D. L. Macalady. 1 9 7 t h . Chemistry of Halogens i n

S e a w a t e r , pp. 161-176. I n R. L. J o l l e y ( e d . ) Water Chlorination:
Enuironmentol Impact and-ZmZth Effects, Vol. 1. Ann Arbor S c i e n c e
P u b l i s h e r s , I n c . , Ann Arbor, Michigan.

C a r p e n t e r , J. H . , and C. A. Sniith. 1978. R e a c t i o n s i n C h l o r i n a t e d Sea-

water, pp. 195-207. I n R. L. J o l l e y , H. Gorchev, and l). 11. Hamiltoir
( e d s . ) Water ChZorina&n: EnuironmentczZ Impact and n e a l t h hyfQCtS,
Vole 2 . A m i Arbor S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor, Michigan.

Chamberlain, N. S., and J. R. Glass. 1943. C o l o r i m e t r i c D e t e r m i n a t i o n

of C h l o r i n e R e s i d u a l s up t o 1 0 ppm w i t h O r t h o t o l i d i n e . ,I. h e r . lJntelr
Works ASSOC, 3 5 : 1205-1221.

Chapin, K. M. 1929. Dichloro-amine. J . A m e r . Chem., SOC. -

51:2112-21-17.

Christman, R. F . , .J. D . Johnson, F. K. P f a e n d e r , D. L. Norwood, M. R. Webb,

J . R. Hass, and M. J. B o b e n r i e t h . 1980. Chemical I d e n t i f i c a t i o n of
A q u a t i c Humic C h l o r i n a t i o n P r o d u c t s , pp. 75-83. I n K. L. J o l l e y ,
W. A . Brungs, and R. B. Cuimuing ( e d s . ) Water Chlorination: Environ-
mental Impact and HeaZth Effects, Vol. 3 . Ann Arbor S c i e n c e P u b l i s h e r s ,
Tnc. , Ann Arbor, Michigan.

C o l t o n , E . , and M. M. Jones. 1955. Monochloramine. J , Chem. Educ. -.32:

.....

485-487.

Connell., C. H . 1947. O r t h o t o l i d i n e T i t r a t i o n P r o c e d u r e f o r Measuring

Chlorine Residuals. J . Amer. Water Works Assoc. - 39:209-219.

Connick, R. E . , and Y . T. Chia. 1959. The H y d r o l y s i s of C h l o r i n e and Its

V a r i a t i o n wi.th Temperature. J. A m e r . Chem. SOC. - 81:1280-1284.

Cooper, W. J . , E. A. S o r b e r , and E. P. Meir. 1975. A Rapid S p e c i f i c F r e e

A v a i l a b l e C h l o r i n e T e s t w i t h S y r i n g a l d a z i n e (FACTS). .J. h e r . Water
Works ASSOC. -- 67 :34-39.

C o r b e t t , R. E . , IJ. S. M e t c a l f , and F. e. S o p e r . 3953. S t u d i e s o f N-

Halogeno-Compounds. IV. The R e a c t i o n Between Ammonia and C h l o r i n e
i n Aqueous S o l u t i o n , and t h e H y d r o l y s i s C o n s t a n t s of Chloramines.
J . C h e m . S O C . , London .___
1953:1327-1929.
 101

C o u r t o t , J . , a n d A. Peron. 1979. Etude Phgsiochimique JL? In L%Zoradian

de Z'eau de mer en Presence d'azote AnunoniacaZ. Nature et E'volzilion
des Haloanlines Formees. Rapport HE/33-79.11 ARD E3EO1, E l e c - t r i c i t e
d e France.

C r a n e , A. M . , P. Kovacic, and E. D. Kovacic. 1980. V o l a t i l e Halocarbon

P r o d u c t i o n from t h e C h l o r i n a t i o n of Marine A l g a l Ryproducts, I n c l u d i n g
U-Mannitol. E n v i r o n . S e i . Technol. 14(11):1371-1374.
I

Crane, C . W . , .J. F o r r e s t , 0 . S t e p h e n s o n , and W. A. Waters. 1'346. The

C h l o r i n a t i o n of Methyl Ui-2-(chlorethyl)amixie and R e l a t e d Compounds.
J. Chem. S o r . , London -___ 1946:827-830.

Cromer, J . L . , G . W. Inman, and .J. D. Johnson. 1978. Dibromnmine Decom-

p o s i t i o n K i n e t i c s , pp. 213-225. I n A. J . Rubin ( e d . ) Chernisery of
Was-t.ewtxf;erTechnnkgy. Ann A r b o r - k i e n c e P u b l i s h e r s , Inc., Ann Arbor,
Michigan a

Czech, F. W . , R. J , Fuchs, and €1. F. Antczak. 1961. D e t e r m i n a t i o n of

Mono-, D i - , and T r i c h l o r a m i n e by U l t r a v i o l e t A b s o r p t i o n Spectro-
photometry. Anal. Chem. - 33:705-707.

I l e i n z e r , M. % F. Schaumburg, and E. K l e i n . 1978. Environmental H e a l t h

S c i e n c e s C e n t e r Task F o r c e Review on Halogenated O r g a n i c s i n D r i n k i n g
Water. Environ. H e a l t h P e r s p e c t i v e s --24:209-239.

Dowell, C. T . , and TJ. C. Bray. 1917. E x p e r i m e n t s w i t h N i t r o g e n

Trichloride. J . A n i e r . Chem. SOC. 39:896-905.

Downs, A . ,J., and I,. .J. Adams. 1973. C h l o r i n e , Bromine, I o d i n e , and

A s t a t i n e , pp. 1170-1594. J. C. Bailar, J r . , H. J . Emeleus,
R. Nyholm, and A . F. Trotman-Dickenson ( e d s . ) C o ~ 2 ~ e h e r ~ O ~~ g~ nvnef c
Chemistry, Vol. 2 , Pergamon Press, I n c . , N e w York.

Drago, R. S. 1957. Chloramine. J Chem. Educ 34:541-545.

D r a l e y , <J. E. 1972. The Treatment of C o o l i n g Water w i t h C h l o r i n e .
ArJLIES-12. Argonne N a t i o n a l L a b o r a t o r y , Argonne, I l l i n o i s .

Edmond, C. R , , and F. G . S o p e r . 1949. The Mechanism of Formation of

UialkyL-Chloramines from Hypochlorous Acid. J. C h e m . S O C . London
---
1949~2942-2945.

E l l i s , A . J., and F. G. Soper. 1954. S t u d i e s o f N-Halogeno Compounds.

VI. The K i n e t i c s of C h l o r i n a t i o n of T e r t i a r y Amines. J . Chem. S o c . ,
r.ondon 1954: 1750-L755.
I_

E I Z m s , .J. W., and S. H. H a u s e r . 1913. O r t h o t o l i d i n e as a Reagent for

t h e C o l o r i m e t r i c E s t i m a t i o n of S m a l l Q u a n t i t i e s of Free Chlorine.
.
Ind. I h g Chem. ___ 5 :915-917
 102

Engel, P . , A. O p l a t k a , and R . Pearlmutter-Hayman. 1954. The Decom-

p o s i t i - o n of Hypohrornite and Bromite S o l u t i o n s - J. A m e r . Chem. Soc.
-76:2010-2015.

Eppley, R. W., E. H. Renger, and P. M. W i l l i a m s . 1976. C h l o r i n e Re-

a c t i o n s w i t h Seawater C o n s t i t u e n t s and the I n h i b i t i o n o f Photo-
s y n t h e s i s o f N a t u r a l Marine P h y t o p l a n k t o n . E s t . C o a s t a l Mar. S c i .
-4 : 147-161.

Farkas, L., M. L e w i n , and R. Bloch, 1949. T h e R e a c t i o n s of H y p o c h l o r i t e

and Bromides. J. A m e r . Chem. SOC. -
71:1988-1991,

F a r k a s , I,. , and M. L e w i n . 1950. The D i s s o c i a t i o n C o n s t a n t f o r Ilypo-

brol-nous Acid. J . A m e r . Chem. S O C . -72:5766-5767.
.

Federal. R e g i s t e r . 1976. Amendments. G u i d e l i n e s f o r E s t a b l i s h i n g Test.

P r o c e d u r e s f o r t h e A n a l y s i s of P o l l u t a n t s . Fed. Reg. - 41(232):5280-
5286 a

Galal-Gorchev, H., and J . C . M o r r i s . 1.965. Formation and S t a b i . l i t y of

Brornamide, Rro-cnimide, and N i t r o g e n Tribromide. i n Aqueous S o l u t i o n .
Inorg, Chem. -4:899-905.

G l a z e , W. H . , F. Y. S a l e h , and W, K i n s t l e y . 1980. C h a r a c t e r i z a t i o n of
N o n v o l a t i l e Halogenated Compounds Formed During Water C h l o r i n a t i o n ,
p p . 99-108. I n R. L . J o l L e y , W. A. Brungs, R. B. Cumming (eds.)
Water ChZorimTion: Environmental Tmpact and IieaZth Effects, V o l . 3.
Ann Arbor S c i e n c e Pub1 i s h e r s , I n c a Ann Arbor, Michigan.

Gmelin. 1969.
C h l o r uncl S t i c k s t o f f , p p . 483-500. Ln GemZin‘s Hnndhuch
der Anorgilnischen Chemie , Achtr Auf l a g e .
C h l o r Eyganzungsband , T e i l
B--T,ieferung 2 , System-nummer 6 . Verlag chemie G . M . B , H . , Weinheim/
Bergs t r .
Gray, E . T . , J r . , D. FJ. Margerum, and R . P . Huffman. 1979. Chloramine
E q u i l i b r i a and t h e K i n e t i c s of D i s p r o p o r t i o n a t i o n i n Aqueous S o l u t i o n ,
p p . 264-277. I n F. E , Bri.nkman and J , M. B e l l a m a ( e d s . ) 0rganometal.s
and Organometanoids, Occurrence and Fate i n t h e Environment. American
Chemical S o c i e t y , Washington, D. C.

Grieve, J . A . , L. E. J o h n s t o n , ‘T. G. D u n s t s a l l , and J . Minor. 1978. A

Program t o Introdiict: S i t e - S p e c i f i c C h l o r i n a t i o n Regimes a t O n t a r i o
Hydro C e n e r a t i n g S t a t i o n s , p p . 77-94. I n K. L . J o l l e y , R. Gorchev,
and D. H. Hamilton, Jr. ( e d s ) W a t m C h z r i n a t i o n : Enviromnerlta~
I

inrpact and Health E f f e c t s , Vol. 2. Ann Arbor S c i e n c e P u b l i s h e r s , I n c . ,

Ann Arbor, Michi gan

G u t e r , K. J., and W. .J. Cooper. 1972. The EvaZuat,ion of Existing F i e l d

T e s t Kits for Determining Free Chlorine ResiduuZs i n Aqueous So Zutious.
U.S. Army Medical Environmental E n g i n e e r i n g R e s e a r c h U n i t , USAYEEKU
Report No. 73-03.
 103

Haag , IJ. 1980a. The Formation of N-bromo-N-chloramines i n Chlorinated

S a l i n e Waters. J. I n o r g . Nucl. Chem. 42~1123-1127.

Haag, W. R. 1980b. Formation o f N-bromo-N-chloramines i n Chlorinated

S a l i n e Waters, pp. 193-201. Tn K. L . J o l l e y , W. A. Brungs, R. B,
Cumming ( e d s . ) Water ChZor<ns?%n: EnvironmentaZ InrpacL und Health
Effects, Vol. 3 . A n n Arl?or S c i e n c e Pub1 i s h e r s , I n c . , Ann A r b o r , Mich.

Haag, W. R . , and L i e t z k e , M. 11. 1980. A K i n e t i c Model f o r P r e d i c t i n g

t h e C o n c e n t r a t i o n s of Active Halogen S p e c i e s i n C h l o r i n a t e d C o o l i n g
Waters, pp. 415-426. I n R. L . J o l l e y , W. A. Brungs, and R. H . Ctimming
( e d s . ) Water C h l o r i n a t z n : EnvironmentaZ Impact and Health Effects,
Vol. 3. Ann Arbor S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor, Miclligan.

Haag, W. R. 1981. On t h e D i s a p p e a r a n c e of C h l o r i n e i n Sea Water. Water

Kes. -
15:937-940.

Haag, W. K. 1981. Oak Ridge N a t i o n a l L a b o r a t o r y . P e r s o n a l communication.

H a l l , T,. W., J r . , G. R. H e l z , and D. T . Burton. 1981. Power PZcrzt ChkW?:-

nation: A 3folo(jic/xZ and Clzemical Assessment. Ann Arbor S c i e n c e
P u b l i s h e r s , I n c . , Ann Arbor, Michigan.

Haller, J. F . , and S. S . L i s t e k . 1948. D e t e r m i n a t i o n of C h l o r i n e D i o x i d e

and O t h e r Active C h l o r i n e Compounds i n Water. Anal. Chem. - 20:639-642.

H a l l i n a n , 17. J . , and W. R. Thompson. 1939. A C r i t i c a l Study of t h e

T h i o s u l f a t e T i t r a t i o n of C h l o r i n e . J . A m e r . Chem. SOC. --.-
61~265-270.

H a l l i n a n , F. J . 1944. Tests f o r Active R e s i d u a l C h l o r i n e and Chloramf-ne

in Water. J. h e r . Water Works Assoc. - 36:296-302.

H a n c i l , V . , and J. M. Smith. 1971. C h l o r i n e - S e n s i t i z e d Photochemical

O x i d a t i o n of S o l u b l e O r g a n i c s i n M u n i c i p a l Wastewater. Ind. Eng.
P r o c e s s D e s . Develop. - l Q ( 4 )3515-523.

H e l z , G. E., and R. Y. Hsu. 1.978a. V o l a t i l e Chloro-Organics and Fromo-

c a r b o n s i n C o a s t a l Waters. Limnol. Oceanogr. 23:858-869. I

H e l z , G. R . , R. Sugam, and R. Y. Elsu. 1978b. C h l o r i n e D e g r a d a t i o n and

Halocarbon P r o d u c t i o n i n E s t u a r i n e W a t e r s , pp. 209-222. In K. L.
J o l l e y , H. Gorchev, and D. H. Hamilton, Jr. ( e d s . ) Va$er ?%~or?hat?:orz:
Environmental. Impact and Health Effects Vol. 2. Ann Arbor Science
.
P u b l i s h e r s , Lnc , Ann A r b o r , Michigan.

H e l z , G , R. 1980. R e s i d u a l C h l o r i n e A n a l y s i s , p p . 363-372. In J. F.
Garey, R. M. J o r d e n , A. H. A i t k e n , D. T. Burton, and R. li.-cray ( e d s . )
Condenser Biofotiling ConkroZ. Ann Arbor Science P u b l i s h e r s , Tnc.,
Ann A r b o r , Michigan.
 1.04

Hoehn, R. C . , C. W. R a n d a l l , R. P. Goode, P. T . R. S h a f f e r . 1978.

C h l o r i n a t i o n and Water Treatment f o r Minimizing T r i h a l o m e t h a n e s i n
D r i n k i n g Water, p p . 519-535. I n R. L. J o l l e y , €3. Gorchev, and D. H.
Hami 1 t o n , Jr. ( e d s . ) Mater C h z z i n a t i o n : hkvironmenta2 Impact and
HealL-h Effgcts, V o l . 2. Ann Arbor S c i e n c e P u b l i s h e r s , I n c . , Ann
Arbor, Michigan,

Hostgaard-Jensen, P . , J . K l i t g a a r d , and K. M. P e d e r s e n . 1977. C h l o r i n e

Decay i n Cooling Water and D i s c h a r g e i n t o Seawater. J . Water P o l l u t .
C o n t r o l Fed. -
49:1832-1841.

Houben, J. , and T. Weyl. 1362. Halogen-verbindungen, pp 7 60-81.1. . In

J . Houben and T. Weyl, Methoden der Organischen Chernie (Houben-Wez)
V i e r t e A u f l a g e , Band 5 , T e i l 3. George T b i e m e V e r l a g , S t u t t g a r t ,

~ ~ ~ g o R.l s S, . , H. A. Wyckoff , T. W. K e t h l e y , R. W. liodgen, E. 1,. F i n c h e r ,

J. C. U i l d e b r a n d , and J. E. Mandel. 1953. B a c t e r i a l S t u d i e s of
Chlorine. Ind. Eng. Chem. 4 5 : 9 6 6 - 1 0 0 0 .
I_

Inman, G. W., T. F. L a P o i n t e , and J . 1). Johnson. 1976. K i n e t i c s of

N i t r o g e n T r i b r o m i d e Decomposition i n Aqueous S o l u t i o n s . i n o r g . Chem.
-
15 :3037-3041.

Tnman, G . W . , and J . D. Johnson. 1978. The E f f e c t of Ammonia Conccn-

t r a t i o n on t h e Chemistry of C h l o r i n a t e d Sen Water, pp. 235-242. In
-
R. L. J o l l e y , H. Gorchev, and D. H. Hamilton, J r . ( e d s . ) $later ChZoi.i-
nation: EnuironmenkaZ 1rnpae-i-and Ileazth Effects, Vol. 2. Ann Arbor
S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor, Michigan.

Inman, G , W . , and J. D. Johnson, 1979. The K i n e t i c s of Hypobromous Acid

Formati-on i n C h l o r i n a t e d S e a Water. P r e p r i n t s of p a p e r s , D i v i s i o n of
Environ. Chem., American Chem. Soc, 1 9 ( 2 ) :68-71.

Isaac, R. A . , and J . C . M o r r i s . 1980. Rates of T r a n s f e r of Act.:i.ve

Chlori-ne Between N i t r o g e n o u s S u b s t r a t e s , pp. 183-191. 7n R. L . J o l l e y ,
W. A. Brungs, and R. B. Cumming ( 4 s . ) Watei. Chlorination-: Environ-
iiientnl Irrrpact and HeaZth Effects, Vol. 3 . Ann Arbor S c i e n c e P u b l i s h e r s ,
I n c . , Ann Arbor, Michigan.

I s a c s s o n , V . , and G. WetLermark. 1976. The Detesiiiination of I n o r g a n i c

C h l o r i n e Compounds by Chemiluminescence R e a c t i o n s . A-ilalytica Chemica
A c t a 83~227-239.
I_

I s a c s s o n , V . , J . Kowalewska, and G. Wettermark. 1 9 7 8 . K i n e t i c i n v e s t i -

g a t i o n s of R e a c t i o n s Between I n o r g a n i c C h l o r i n e Compounds and Luminol.
J . h o r g . Nucl. Chem. 40:1653-1656.
I_

I s a c s s o n , V . , and G. Wettermark. 1978. S e l e c t i v e A n a l y s i s o f C h l o r i n e

(Hypochlorous Acid) and C h l o r i n e D i o x i d e Using Cbemiluiiii~nescence.
A n a l y t - i c a l L e t t e r s __
A11(1):13-25.
 105

J a n d e r , J. 1955a. E i n B e i t r a g z u r K e n n t n i s d e s Monochloramins.
N a t u r w i s s e n s c h a f t e r n .4- 2 ~ 1 7 8 - 1 7 9 .

J a n d e r , J. 1955b. Zum V e r s t a n d n i s d e r Chemie d e r C h l o r - S t i c k s t o f f -

Verbindungen. Z. Anorg. Allgem. Chem. 2802276-283.

Johnson, J . D . , and K. Overby. 1969. S t a b i l i z e d N e u t r a l O r t h o t o l i d i n e ,

SNORT, C o l o r i m e t r i c Method f o r C h l o r i n e . A n a l . Chem. - 41(13):1744-
1750.

Johnson, J . D . , and R. Overby. 1 9 7 1 . Bromine and Bromamine D i s i n f e c t i o n

Chemistry. J . S a n i t . Eng. Div. ASCE - 97:617-627.

Johnson, J . D . , and J . W. Edwards. 1974. An Amperometric Membrane

Halogen A n a l y z e r , P r e p r i n t s of P a p e r s , D i v i s i o n of Environmental
C h e m i s t r y , American Chemical S o c i e t y --1 4 (1):169-173.

Johnson, J . D . 1977. A n a l y t i c a l Problems i n C h l o r i n a t i o n of S a l i n e Water.

Chesapeake Sci.. l 8 ( 1 ) :116-118"
I.___

Johnson, .I. D. 1978a. Measurement and P e r s i s t e n c e of C h l o r i n e R e s i d u a l s

i n N a t u r a l Waters, p p . 37-63. I n R. L . J o l l e y ( e d . ) Wader ChZori-
nation: Environmental. -1mpac-t? n
a f l e u l t h Effects, V o l a 1. Ann Arbor
S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor, Michigan.

Johnson, J . D e , J . W. Edwards, and F. Keeslar. 1978. Chl.orine R e s i d u a l

Measurement C e l l : The H O C 1 Membrane E l e c t r o d e . J. A m e r . Water Works
ASSOC. 70: 341-348.

Johnson, J. D. 1981. U n i v e r s i t y of North C a r o l i n a , Chapel H i l l , N . C . ,

p e r s o n a l communication.

J o l l e y , R. T.,. 1973. CLorination Effects on Organic Constituents in

E f f l u e n t s $porn Domestic Sunitmy Sewage Treatment Plants. OIWL/TM-
4290. Oak Ridge N a t i o n a l L a b o r a t o r y , Oak Ridge, Tennessee,

J o l l e y , R. L . 1978. Water Chlorination: Environmental Impact mmd Health

E f f m t s , Vol. 1. Ann Arbor S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor,
Michigan. 439 p. S u p p l i e d as CONF75109b.

J o l l e y , R. L . , G. J o n e s , W. W. P i t t , and J . E. Thompson. 1978a. C h l o r i -

n a t i o n of O r g a n i c s i n Cooling Waters and P r o c e s s E f f l u e n t s , pp. 105-
138. I n R. I,. J o l l e y (ea. ) Water Chlorination: Environmentozl I m p c t
and IIeTrth Effects, V o l . 1. Ann Arbor S c i e n c e P u b l i s h e r s , Lnc.,
Ann Arbor, Michigan.

J o l l e y , R. L . , H. Gorchev, and D. H. Hamilton, J r .

1978b. Wuter Chlori-
na-kion: Env~rorzment-alImpact m d Wecilth Effects , Vol. 2 . Ann Arbor
S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor, Michigan.
 106

Jolley, R. L., W. W. Pitt, Jr., F. G. raylor, Jr., S. J. Hartmann,

G , Jones, Jr., and .J, E. Thompson. 1978c. An Experimental hssess-
mexit of Halogenated Organics i n Waters from Cooling T o w e r s and Once-
Through Systems, p p . 695-705. In R. L. Jollcy, H, Gorchev, D. H.
I-Iamilton,Jr. (eds.) Water Chlorinution: Enuironmerztal Inpact and
Health E f f e c t s , Vol.. 2 . Ann Arbor Science Publishers, Inc., Ann
Arbor, Michigan.

Joll.ey, R. L . , W. A. Brungs, and R. B. Cumming. 1980. Vater ChZorination:

hkuironmentczl Impact and Health Effects, V o l . 3. Ann Arbor Science
Publishers, Inc., Ann Arbor, Michigan.

Khalanski, M. 1980. Donnees sur Z'evoZut,ion de l a teneur en o x y d m t

residueldaas des echartillons d'eau de mer chloree. Electricite de
France, Report IIE/31-79.26 ARD E3D02, Chatou, France.

Kovacic, P., M. Lowery, and K. W. Fie1.d. 1971). Chemistry of N-bromamines

and N-chloramines. Chem. Rev. 70:639-665.

LaPointe, T. F., G. Inman, and J. D. Johnson. 1975. Kinetics of Tri-

bromamine Decomposition, pp. 301-338. In J. D. Johnson (ed.)
Disinfection Water cnzd Mastewater. AnnTrbor Science Publishers,
Inc., A n n Arbor, Michigan

Latimer, W. M., and J. [I. Hildebrand. 1940. Reference Book oJ I n o r g m i e

Chemistry. The MacMillan Co. , New York -
Lewin, M., and M. Avrahami. 1955. The Decomposition of Hypochlorite--
Hypobromite Mixt-ures in the pB Kange 7-10. J. h e r . Chem. S O C . 77:
4491-4498.

Lieberman, J., Jr., E. P. Meier, W. J. Cooppr, arid N. M. Roscher. 1978.

Modified FACTS Test Procedures for Disinfectants Other 'Than Free
Available Chlorine. Combined Chlorine and Ozone. Preprints of
Papers, Division of Environmcneal Cheiaistry, American Chemical
Society 18(1):15-16.
-

Lieherman3 J., Jr.,.N. M. Roscher, E. P. Meier, and W. J. Cooper. 1980.

Development of the FACTS Procedure for Combiized Forms of Chlorine
and Ozone in Aqueous Solutions. Environ. Sci. Techno1 .14......(11):
e

1395-1400.

Lietzke, M. H. 1978a. A Kinetic Model f o r Predicting the Composition

of Chlorinated Watrr Discharged from Power Plant Cooling Systems,
p p . 367-378. In R. L. J o l l e y ( e d . ) Water C'hZorination: Znviron-
mental Irrripact UTd Health E f f e c t s , Vol. 1. Ann Arbor Science Pub-
lishers, Inc., Ann Arbor, Michigan.

Lietzke, M. H. 19781,. A Kinetic Model for Predictirlg the Composition of

Chlorinated Water Discharged f r o m Power Plant Cooling System, pp.
707-716. In R. L. Jolley, H. Gorchev, D. 11. Hamilton, Jr. (eds.)
Water ChZoG&xtion: h'nvironrnental Impact and Health Effects, V o l . 2.
Ann Arbor Science Publishers, Inc., Ann Arbor, Michigan.
 1 07

L i s h k a , R. .J., E . F. McParren, and .J. H. Parker. 1969. Wakeitl C?~7,owhe

(Residual) No. I , Study Number 35. U , S . Department of t I e a l t h ,
E d u c a t i o n and Welf arc, Piibl-ic Health Service.

L i s h k a , R. J., and E. F. McFarren. 1971. b?df;er>Chbr.!:ne (fles<dual)

No. 2 , R e p o r t Number 4 0 . Environmental P r o t e c t i o n Agency.

L i s t e r , M. W. 1956a. Decomposition of Sodium I l j j p o c h l o r i t e : The

Uncntalyzed R e a c t i o n . Can. .I. CI-ncm. -
34 :465-478.

L i s t e r , M. IJ. 1956b. Decompos-ition of Sodium H y p o c h l o r i t e : The

Catalyzed Reaction. Can. J . Chem. 34:479-488. I

L i s t e r , M. W., and R. C. P e t t e r s o n , 1962. Oxygen E v o l u t i o n from Sodium

H y p o c h l o r i t e S o l u t i o n s . C a n . J. Chem. 40: 729-733.

L i s t e r , M. W . , and P. Kosenblum. 1963. Rates of R e a c t i o n of H y p o c h l o r i t e

I o n s w i t h S u l f - i t e and loclide Ions. Can. J . Chem. 41:3013-3020.
I_

Macalady, D. L $ , J. H. C a r p e n t e r , and C. A, Moore, 1977. S u n l i g h t -

Induced Bromate Formation i.n C h l o r i n a t e d S e a w a t e r * Science -
195 :
1335-1337.

Manabe, R. M. 1.974. bleasurerrien?; oJ’Residual C??%oririeLaic l s in i:oo l i n g

Mz ter--Amy, emme tr i e Me thod .
E‘? R 6 6 0 / 2 - 7 3 - 0 3 9

Margerum, D. W . , E . ‘T. Gray, Jr., and R, I?. Huffman. 1979. C h l o r i n a t i o n

and t h e Formation of N--chloro Compounds i n Water Treatment:, p p . 278-
291. - I n 1;. E. Krinclunan and .T. M. Belloma ( c d s . ) Oryanornetu~sand
Organornetal l o i J s , Occurrmce and Fate in t h e Emiroriment. American
Chemical S o c i e r y , IzTnsbington, D.C.

Marienko, G . 1980. Workshop on Detemnination ( ~ Chlorine

f in Seavatrp
MatrZz. AS’1’M Report No. RR:D19-1067. American S o c i e t y f o r Testing
Materials, P h i l a d e l p h i a , Permsylvania.

Pfarienko, G . , R. J. H u g g e t t , and D. G . F r i e n d . 1975. An .Trzstrurncnt W?:th

.patemu Z. Ca I tbratiow, f o r izbn itoring l.71lor.l:ne Residua I s in f l ~ t u rZn
V a t e r s . National. Bureau of S t a n d a r d s 81’-255829,

Marienko, G . , R. J. H u g g e t t , and D. G. F r i e n d . 1976. A n Instrumect With

Inter r i a l C a l . ib r nt i o n f o r Monj. t o r irig C h L o r line Xes i d u d c; i.t i N a t u ra.1.
bJaters, J. F i s h Res. E d . Can. .3.3:622-826.

PIarks, N. C. 1972. I i e s i d u a l C h l o r i n e Analysis i n Water and Waste Water,

p p . 1213-1247, 111 L. L. c i a c c i o ( e d . h k t c r and blut$:r PolZut-io?t
I

linndbook Marcel I k k k e r I n c . New York.

~

Marks, El. C . , and J.. R. Glass. 1942. A N e w Method of Determining

Residual. CX13orine. J. Amer. Water Work:; Assoc. -_-
3 4 : 1227-121rO.
 108

Marks, 11. C., D. B. W i l l i a m s , and G. V . Glasgow. 1951. D e t e r m i n a t i o n

of R e s i d u a l C h l o r i n e Compouuds. J. A m e r . Water Works Assoc, 4 3 :
201-207.
L

Mauger, K. P . , and F. G. Soper. 1946. Acid C a t a l y s i s i n the. Formation

of Chloramides from Hypochlorous Acid. J. Chem. SOC. - 1946:71-75.
.

McKee, J . E . , C . J . Rrokaw, and R. T . McLaughlin. 1960. Chemical and

C o l i c i d a l E f f e c t s of Halogens i n Sewage. J. Water P o l l u t e C o n t r o l
Fed. 3 2 ~ 7 9 5 - 8 1 9 .
I

M e t c a l f , W. S . 1342. The A b s o r p t i o n S p e c t r a of Mono-, D i - , and T r i -

Chloramines and Some A1iphati.c D e r i v a t i v e s . J . Chem. S O C . , London
1942:148-150.
.._

Minear, R. A . , and J . C. B i r d . 1980. r r i h a l o m e t h a n e s : I m p a c t of Bromide

con C o n c e n t r a t i o n on Y i e l d , S p e c i e s D i s t r i b u t i o n , Rate of Formation
and I n f l u e n c e of O t h e r V a r i a b l e s , pp. 151-160, tn R . T,. J o l l e y ,
W. A. Brungs, R. R , Cumming ( e d s . ) Water Chlorinution: En?kvwx?ntaz
ii?ipnct and Hea l t h E f f e c t s , V o l . 3. Ann Arbor S c i e n c e P u b l i s h e r s , I n c . ,
Ann Arbor, Michi e m .

M o r r i s , J. C. 1966. 'I'he Acid I o n i z a t i o n C o n s t a n t of HOC1 from 5 t o 35°C.

70: 3798-3802,
.J. Pliys. Chem. -

M o s r i s , J. C . 1967. K i n e t i c s of R e a c t i o n s Between Aqueous C h l o r i n e and

N i t r o g e n o u s Compounds, pp. 28-53. I n S. 1). F o u s t and J. B. Hunter
( e d s . ) Pmhcipals and Applications of Water Chernistq. .John Wiley
an3 Sons, New York.

M o r r i s , J . C. 1975. Fou;ination of IlaZogenated Organics by Chlorination

of WclLer Supplies ( A Review). EPA-600/1-75-002, U . S. Environmental
P r o t e c t i o n Agency.

M o r r i s , J . C. 1978a. The Chemistry of Aqueous C h l o r i n e i n R e l a t i o n t o

Water C h l o r i n a t i o n , p p . 21-35. I n K. I,. J o l l e y ( e d . ) Vatez. Chlori-
nukion: Bzvironmental lmpacL anz-flealth E f f e c t s , Vol, 1. Ann Arbor
S c i e n c e P u b l i s h e r s , i n c . , Ann Arbor, Michigan.

M o r r i s , J. C . 1978b. Modem Chemiccxl Me6hod.s in Water and Waste Treat-

ment, V o l . I , IntemationuZ Course i n Sanitayy Engineering. I n t e r -
n a t i o n a l I n s t i t u t e f o r H y d r a u l i c and Environmental E n g i n e e r i n g .
D e l f t The N e t ' n r r l a n d s
~ e

M o r r i s , J. C . , and R . Raum. 1978. P r e c u r s o r s arid Mechanisms of I l a l o f o r m

Forination i n t h e C h l o r i n a t i o n of Water S u p p l i e s , pp. 29-48. In
R. I,. J o l l e y , H, Gorchev, and D. H. Hamilton, J r . ( e d s . ) FlaterChZori-
-mtCon: Environmental I q a c t and Health E f f e c t s , Vol. 2 . Ann Arbor
Science P u b l i s h e r s , I n c . , Aiiii Arbor, Michigan.
 109

N. Ram, B. B a r n , and E. Wajon. 1980. Foiamation arid Siy-

M o r r i s , J. C . ,
niSicixnce of N-chlnrv Corrpound;. lin Vatei. S u p p l i h v . EPA-600/2-80-031.
U.S. Environmental P r o t e c t i o n Agency.

Morrow, J. J. 1966. R e s i d u a l - C h l o r i n e D e t e r m i n a t i o n With Dual P o l a r i z a b l e

Electrodes -
J. A m e r . Water Works Assoc. - 58 :363-367.

Morrow, J. J . , and R. N . Roop. 1975. Advances i n C h l o r i n e R e s i d u a l

A n a l y s i s . ,J A m e r . Water Works Assoc. 67 :184-186. I-

N i c o l s o n , N . .J. 1965. An E v a l u a t i o n of t h e Methods f o r Determinjng

R e s i d u a l C h l o r i n e i n Water. The A n a l y s t 90(1069):187-198.
I_

Olson, R., and D. T. W i l l j a m s . 1980. Assessment of Some Aqueous R e s i d u a l

C h l o r i n e Measurements. B u l l . Environ. Contam. T o x i c o l . 24:%51-256. _I

~ p r e s k o , D. M. 1980. Kevitlu of open Literaahwe on E f p c j t s of Chlorine

on Aquatic Organisms. E l e c t r i c Power Research I n s t i t u t e EA-I 491.

P a l i n , A. T. 1954. Determining R e s i d u a l C h l o r i n e i n Water by N e u t r a l

O r t h o - T o l i d i n e Methods. Water i311d Sewage Works 1 0 1 : 74-76.

P a l i n , A . T. 1957. The D e t e r m i n a t i o n of F r e e and Combined C h l o r i n e i n

Water by t h e U s e of Diethyl-p-phenylene D i a l n i n e . J. A m e r . Water Works
ASSOC. ___
49~873-880.

P a l i n , A . T. 1975. Water D i s i n f e c t i o n , Chemical A s p e c t s and A n a l y t i c a l

C o n t r o l , pp. 67-89, I n J. D. Johnson ( e d . ) D i s i n S ~ c t , ~ o n - - ~ ~and ~ter
Wastewater. Ann Arbor--Science P u b l i s h e r s , I n c . , Ann Arbor, Michigan.
P a l i n , A . T. 1978. A New DPD-Steadifac Method f o r t h e S p e c i f i c D e t e r m i -
n a t i o n oi: Free A v a i l a b l e C h l o r i n e i n t h e P r e s e n c e of High Monochlor-
amine. J. I n s t . Water Erigrs. and S c i e n t i s t s 32:327-328. I-

P a l i n , A. T. 1980. A n a l y t i c a l Note: A New DPD-Steadifnc Method f o r

S p e c i f i c D e t e r m i n a t i o n of Free A v a i l a b l e C h l o r i n e i n t h e P r e s e n c e of
High Monochloramine .
) .I A m e r Water Works Assoc. - 72 :121-122.

Payne, J . T. 1979. Performance C h a r a c t e r i s t i c s o f an Amperometric

Titrator. J . Water P o l l u t . C o n t r o l Fed. -
51(6):2540-2544.

Peters, C. J . , K. 3 . Young, a n d R. P e r r y " 1980. F a c t o r s I n f l u e n c i . n g t h e

Formation o f Haloforms i n t h e C h l o r i n a t i o n of Humic Materials, E n v i r o n .
S c i . Technol. _-
1 5 (11):l39L-1395.

1978. Yhe Aqueous C h l o m h i x - ! & m of OrgunAic Corrpounds:

P i e r c e , R. C.
Chem&xi! R e m t i . v i t g tmd E f f e c t s oz Environments Z. Q m l i t y . NxCC
16450. N a t i o n a l R e s e a r c h C o u n c i l , O t t a w a , Canada.

P r e s s l e y , T. A . ,
D. F. Rishrjp, A. P. Pi.nto, and A . F. C n s s e l . 1.973.
Amonitz-iVl trogen Rerriovill by Breakpoint ChZoP~rmt i c i n , EPA-57012-73-
058. U. S. Environmei-~talP r o t e c t t o n Agency.
 110

R i c e , J. K . , Id. A. Keilbaugh, W. J . Merz, and P. S. S o l t i s . 1980. Over-

a l l P r e c i s i o n o f t h e Amperometric Method of T e s t f o r C h l o r i n e i n Water,
pp. 383-393. I n 3. F. Garey, R. M. J o r d a n , A. II. A i t k e n , 1). 'i'.
B u r t o n , and R . T . Gray ( e d s . ) Condenser BiofomZing Control. Ann Arbor
S c i e n c e P u b l i s h e r s , rnc. Ann Arbor, Michigan.

Rickabaugh, J. F . , and R. M. Kinman. 1978. T r i h a l o m e t h a n e Formation

from I o d i n e and C h l o r i n e D i s i n f e c t i o n of Ohio River Water, pp. 583-
591. In K. L. J o l l e y , H. Gorchev, and D. H. Hamilton, Jr. ( e d s , )
Flater ?%ZorCnation: Environmental Impact and Hea Zth E f f e c t s , Vol. 2.
Ann Arbor S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor, Michigan.

Rigdon, 1,. P . , G. J . Moody, and J . W. F r a z i e r . 1978. D e t e r m i n a t i o n of

R e s i d u a l C h l o r i n e i.n Water w i t h Computer Automation and a R e s i d u a l -
C h l o r i n e E l e c t r o d e . Anal. Chem. 50(3):465-469.

Kook, J . J . 1974. Formation of Haloforms During C h l o r i n a t i o n of N a t u r a l

Waters. Water T r e a t . Exam. 23 (2) : 234-243

Rook, J. J . 1980. P o s s i b l e Pathways f o r t h e Foriuation o f C h l o r i n a t e d

D e g r a d a t i o n P r o d u c t s During C h l - o r i n a t i o n of Humic Acids and Resor-
c i n o l , pp. 85-98. I n R. 1,. J o l l e y , W. A. Brungs, R. B. Curnni:i.ng ( e d s . )
..~-...

Water Chlorination: Environmental .rmpact and Health Effecks, V o l . 3.

Ann Arbor S c i e n c e P u b l i s h e r s , I n c . , Ann A r b o r , Michigan.

Rosclzer, N. M . , E. H a l l , B. Rosenthal., W. J. Cooper, and E. P. Meier.

1980. CompnrCson of FACTS and DP3-STEADIFAC Procedures for Free and
Combined Chlorine i n Aqueous Solut-ion. F i n a l R e p o r t , U. S. Army Medical
B i o e n g i n e e r i n g Research and Development Lab., F t . D e t r i c k , F r e d e r i c k ,
Maryland, AD AQ90765.

Ryan, E. E . , W. J. Cooper, E. P. Meier, and D. W. R o s e n b l a t t . 1.980.

Development of FACTS Procedures for Bpomine, Chlorine Dioxide, and
iodine i n Aqueous Solutions. T e c h n i c a l Report 8003, U.S. Army
Medical B i o e n g i n e e r i n g Research and Development Lab., Ft. Iktrick,
F r e d e r i c k , Maryland, AD A091590.

S a f e Drinki-ng Water Committee. 1980. Drinking Water and HealL-h, V o l . 2.

N a t i o n a l R e s e a r c h Couizcil.. N a t i o n a l Academy P r e s s , Washington, D. C.

S a g u i n s i n , J . L. S . , and .J. C. M o r r i s . 1975. The Chemistry of Aqueous

N i t r o g e n C h l o r i d e , pp. 277-299. Tn J . D. Johnson (ed. ) Disihfection
Water and Flastewater. Ann Arbor 'Science P u b l i s h e r s , I n c . Ann Arbor,
Michigan.

Sandford, P. A . , A. J. N a f z i g e r , and A. J e a n e s . L97L. R e a c t i o n of

Sodium H y p o c h l o r i t e w i t h Amines and Amides: A New Method f o r
Q u a n t i t a t i n g Amino S u g a r s i n Monomeric Form. Anal, Biochem. 42:
422-436.
 111

S c a r a n o , G . , and M. G . S a r o g l i a . 1980. R e s i d u a l Chlori-ne A n a l y s i s :

A Comparison Between Amperometric and P o t e n t i o m e t r i c Methods, pp. 373-
381. I n J . G. Garey, R. M. J o r d e n , A . H. A i t k e n , D. ‘I’. B u r t o n , and
R. H. c a y ( e d s . ) Condanser B?kfouZ,<,ngControl, Ann Arbor S c i e n c e
P u b l i s h e r s I n c . , Ann A r b o r , Michigati.

Seaman, C. V . , B. B. F l o r a 11, arid R. A . H i l t u n e n . 1980a. M o n i t o r i n g

C h l o r i n a t e d D i s c h a r g e s w i t h Automated I n s t r u m e n t a t i o n , p p . 255-262.
In K. L. J o l l e y , W. A. Brungs, arid R. B. Cumming ( e d s . ) Watez. ChloFi-
I

nation: Enm:ronmentnl T’vtpnr:t and fleii Ith Effects, vel. 3. Ann Arbor
S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor, Michigan.

Seaman, C. V . ,8. B. F l o r a If, and R. A . I l i l t u n e n . l980b. M ~ t h o d sJ@OP

Monitoring ChZorinated Discharges. Tennessee V a l l e y A u t h o r i t y EDT-100.

S e i t z , W. R. 1975. Chemiluminescence from t h e Reaction Between Hypo-

c h l o r i t e and Luminol. J. Phys. Chem. 7c)(2) : l O l - l 0 6 .
-I^

Sengupta, C . , G. R. Helz, J. W. Get-z, P. H t g g i n s , J , C. P e t e r s o n , A . C.

S i g l e o , and R. Sugam. 1978. Szlrvs,7j of C h b r i n e A n l x l y t z k l Methods
S u i t a b l e fora t h e Power Industry. E l e c t r i c Power R e s e a r c h I n s t i t u t e
EA-929.

Smith, J . H . , D. C. Bomberger, J r . , and D. L. Haynes. 1980. P r e d i c t i o n

of t h e V o l a t i l i z a t i o n Rates o f H i g h - V o l a t i l i t y Chernica.Ls from N a t u r a l
Water Bodies. Environ. S e i . ‘Cechnol. 14(11):1332-1337.

Snead, M. C . , V. P. O l i v i e r i , and W. H. Dennis. 1981. B i o l o g i c a l Evalu-

a t i o n Plethods f o r t h e D e c e r m i n a t i o n o f F r e e A v a i l a b l e C h l o r i n e , p p .
401-427. I n W. J . Cooper (ea.) C h m r k t r y i n Gdater Reuse, Ann Arbor
S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor, Michigan.

S o d e r b e r g , J. R . , C. Baer, J . D. Johnson, and D. R o s e n b l a t t . 1980.

T e s t i n g a P o r t a b l e P o l a r o g r a p h i c E l e c t r o d e € o r t h e Measurement o f
HOC1 and fi’ree A v a i l a b l e C h l o r i n e , p p . 239-254. I n R . L. J o l l e y ,
W. A. Brungs, and R . B. Cuniming ( e d s . ) Water ChZz&wt&m: Euiliron-
mental Impact and Health h ’ f f e e t s , Vol. 3. Ann Arbor S c i e n c e Pub-
l i s h e r s , Inc., Ann Arbor, Michigan.

S o l l o , F. W., and T. E. L a r s o n , 1965. D e t e r m i n a t i o n of F r e e C h l o r i n e

by Methyl Orange. 3 . Amer-. Water Works Assoc. - 57:1575-1..585,

S o l l o , F. b7., F. F. McGurk, and T. E. L a r s o n . 1970. S t a t u s of Methods

f o r Halogen D e t e r m i n a t i o n . (Rr-CP) , p p . 245-267 I n E-’meeed.ings of
t h e iV&iom% L9pecZaZty Conference on, D i s i n f e c t i o n , American S o c i e t y
o f C i v i l E n g i n e e r s , New York,

S o r b e r , C . , W. Cooper, and E. Meier. 1.977. S e l e c t i o n of a F i e l d Method

f o r Free Avail.able C7nlori.ne9 p p . 91-112. I n J. D. Johnson ( e d . )
. A r b o r Science P u b l i s h e r s ,
U i c i n f e c t i n n Wcz-ter and Vas t - . s ~ ~ t e rAnn
Pnc., Ann A r b o r , Michigan.
 112

Starzclard Methods f m the Examination of Water and Wastew&er, 1 4 t h Ed.,

Aiiierican P u b l i c H e a l t h A s s o c i a t i o n . 1975.

S t e v e n s , A. A . , C. J . Slocum, D. R. S e e g e r , and G . G . Robeck. 1978.

C h l o r i n a t i o n of O r g a n i c s i n D r i n k i n g Water, pp. 77-104. I n R. I,.
J o l l e y (ed ) Water ChZorination: Environmental I q n c f ; ond->ieal t h
a

Effects, Vol. 1. Ann Arbor S c i e n c e P u b l i s h e r s , Ann Arbor, Michigan.

S t o c k , J . T. 196.5 Ampemmetric T-ztv3at.ions Interscience Publishers,

N e w York.

Sugaim, R . , and G. R. H e l z . 1980. Seawater C h l o r i n a t i o n : A D e s c r i p t i o n

of Chemical S p e c i a t i o n , p p . 427-433. I n R. L. J o l l e y , W. A. Brungs,
and R. B. Cumrning ( e d s . ) Water C h l o r i n z i o n : Environmentul I m p m i
and f i e u l t h Effects, V o l . 3. Ann Arbor S c i e n c e P u b l i s h e r s , I n c . ,
Ann Arbor, M i c h i gan.

Sugaiii, R . , and G . R. Welz, 1977. S p e c i a t i o n of C h l o r i n e Produced O x i d a n t s

in Marine Waters. Chesapeake Sci. 18:113-J-l.5. L

Sugam, R . , and G. R. Helz. 1981. C h l o r i n e S p e c i a t i o n i n Seawaters,

A M e t a s t a b l e Equi.1 ibrium Model f o r C1' and B r L S p e c i e s . Chemosphere
10:41-57.
-

Sugam, R . , W. S w a l l o w , and J. T r o u t . 1981. Field Eiinlzlation o f Chlorine

Monitoring TecJmiques. EPRL EA-2070. E l e c t r i c Power Research I n s t i t u t e .

Symons, J. M . , T. A . B c l l a r , J . K. C a r s w e l l , J. Uemarco, K. T,. K r o p p ,

G. G. Robeck, D. R. S e e g e r , C. J. Slocum, R . 1 , . Smith, arid A. A.
Stevens. 1975. N a t i o n a l O r g a n i c s R e c o n n a i s s a n c e Survey f o r Nalo-
gcnated Organics i n D r i n k i n g Water. J . A m e r . Water Works Assoc. _6 -7-:
6311-647.

T a r a s , M. J . 1950. P r e l i m i n a r y S t u d i e s i n t h e C h l o r i n e Uemarid of
S p e c i f i c Chemi-cal Compounds. J . A m e r . Water Works Assoc. - 4 2 :462-474.

Taras, M. J. 1953. E f E e c t o f F r e e R e s i d u a l C h l o r i n a t i o n on Ni-trogen

Compounds i n Water. J . A m e r . Water Works Assoc. 45:47-61.

' T h e i l a c k e r , W. , and E. Wegner. 1964. O r g a n i c S y n t h e s e s Using Chloramine,

p p . 303-317. I n W. F o e r s t ( e d . ) Newer Methods o f Preparative Organic
Chernistyy . (Tkynsl by W. Birnbaum. ) Academic Press Tiice, N e w York.

Thomas, R. F . , M. J . Weisner, and H. J . Brass. 1980. The F i f t h T r i h a l o -

methane: Dichl.oroiodomethane, I t s S t a b i l i t y and Occur~-enc:es i n
C h l o r i n a t e d D r i n k i n g Water, pp. J-61-168. 1.n R . L . J o l l e y , W. A.
Brungs, and R. B. Gumming ( e d s . ) Vater ChZi-&nation: Environmental
Tnpact and Health EffecAs, Vol. 3 . Ann Arbor S c i e n c e P u b l i s h e r s ,
I n c . , Ann Arbor, Michigan.

T r o f e , T . W . , G . W. Inman, and J . D. Johnson. 1980. K i n e t i c s of Mono-

c h l o r a m i n e Decoiuposit ion i 11 t-he P r e s e n c e o f Bromide. Environ. S c i .
Technol.. - 1 4 ( 5 ) :544-549.
 113

U t i l i t y Water A c t Group. 1979. C o l l a b o r a t i v e T e s t R e s u l t s f o r C h l o r i n e

A n a l y s i s by Amperometric T i t r a t i o n . R e p o r t .

Wajon, 3 . E . , and J. C. M o r r i s . 1980a. Bromamination Chemistry: Rates

of Formation of N H 2 B r and Some N-bromoamino A c i d s , p p . 171-181.. -In
R. L. J o l l e y , W. A. Brungs, and R. B. C u m i n g ( e d s . ) VaCer ChZori-
nation: Env<mnmcntal h p a c t and Health Effects, Vol. 3 . Ann Arbor
S c i e n c e P u b l i s h e r s , I n c . , Ann Arbor, Michigan.

Wajon, 3 . E . , and 3 . C . M o r r i s . 1980b. The A n a l y s i s of F r e e C h l o r i n e

i n t h e P r e s e n c e of N i t r o g e n o u s O r g a n i c Compounds. Environ. I n t e r -
national - 3:41-47.

Wei, I. W . , and 3 . C. M o r r i s . 1 9 7 4 . Dynamics o f B r e a k p o i n t C h l o r i n a t i o n ,

p p . 297-232. I n A. J . R u b i n ( e d . ) C h e r n i w t q of bkzter Supply, T ~ e a t -
men&, and D<st'ri&ut<on. Ann Arbor S c i e n c e P u b l i s h e r s , Tnc. , Ann Arbor,
M ich i g an.

Weil, I . , and J. C. M o r r i s . 1949a. K i n e t i c S t u d i e s on t h e Chloramines.

I. The Rates of Formation of Monochloramine, N-chloromethylamine, and
N-chlorodirnethylamine. J . hmer. Chem. SOC. z : 1 6 6 4 - 1 6 7 4 .

Weil, I . , and .J. C . M o r r i s . 194%. E q u i l i b r i u m S t u d i e s on N-chloro Com-

pounds. 11. The Base S t r e n g t h of N-chloro D i a l k y l a m i n e s and oE
Monochloramine. J. Amer. Chem, Soc. 2:
31-23-3126.

White, G. C. 1972. D e t e r m i n a t i o n of C h l o r i n e R e s i d u a l s i n Water Treat-

ment, pp. 228-277. Htxndbook of ChLor<nnt?h. Van Nostrand Reinhold
C o . , New York.

White, G. C. 1972. Flcrndbook of Chlorination. Van Nostrand Reinhold

Co., New York.

W h i t t l e , G. P., and A. L a p s t e f f , . J r . 1975. New Ana1yt::i.eal Techniques

f o r t h e Study of Water D i s i n f e c t i o n , pp. 63-88. I n A. J. Rubin (ed.)
Chemistry of W0te.r Supply9 Xmatment, and Di&z?&?&on. Ann Arbor
S c i e n c e P u b l i s h e r s , I n c . , Ann A r b o r , Michigan.

W i l I a r d , H. H . , L. L. Merritt, J r . , and J . A . Dean. 1965. Tnstr-menta%

Methods of RnaZysis, 4 t h Ed. D . Van Nostrand C o n , I R C . , P r i n c e t o n ,
New Jersey.

Wong, G . T . F. 1980. The E f f e c t s of L i g h t on t h e D i s s i p a t i o n of C h l o r i n e

in Seawater. Water Res. - 14:1263-1268.

Wong, G . T. F . , and 3 . A. Daviclson. 1977. The F a t e o f C h l o r i n e i n Sea-

water. Water Res. - 11:971-978.

Wong, G. T . F . , and P. G. B r e w e r . 1 9 7 7 . 'rhe Marine Chemistry of I o d i n e

i n Anoxic B a s i n s . Geochim. Cosmochim. Acta - 41:151-159.
 114

Wri-ght, N. C. 1926. The Action of Hypochlorites on Amino Acids and

Proteins. Biochern. J. --2 0 : 5 2 4 - 5 3 2 .

Wright, N. C. 1936. The Action of Hypochlorites on Amino A c i d s and

Proteins. The Effect of Acidity and Alkalinity. Biochern. J. - 30:
1661-1667.
 115

ORNL/TM-7788

INTERNKL D IS TRIBUTPQN

1. W. D. Rostick 36. D. E. Reichle

2. D. 0. Campbell 37 - .J. W. Roddy
3 . D. A . Costanzo 38. e. D. Scott
4 . C. C. Coutant 39 L F. G. Seeley
5. K. E. Cowscr 40-42. C. H. Shappert
6 . W. Fulkerson 43-47. S. E. Shumate
7-11. R. K. Genung 48. S. P. N. Singh
12. W. R. Haag 49. G. W. Strandberg
13. J . D. Hewitt 50. J. R. Trabalka
14-18. J. K. Nightower 51. S . C. Tsai
19-28. R. L. Jolley 52 * S. K. Whatley
2 9 . C. E. Lamb .53. B. E. Z i t t e l
30. N. E. Lee 54-55. Laboracory Records Department
31. M. H. Lietzke 56. Laboratory Records, RC
32. J. E. Flrochek 57 ORNL Patent Section
I

33. D. E. Opresko 58-59. Central Research Library

34. J. J. Perona 60. ORNL-Y-12 Technical Library
35. IJ. w. Pitt Document Reference Section
61. W. R . Corcoran (consultant)

EXTERNAL DI S'L'RIBUT
ION

62. Office of Assistant Manager, Energy Research and Development,

DOE-ORO, P. 0 . Box E, Oak Ridge, TN 3 7 8 3 0 .
63 Nathaniel Barr, Department of Energy, EV-34, CTN, Washington,
D.C. 20545.
64. Robert W. Brocksen, Electric P o w e r Kesearch Institute, P. 0. Box
10412, Yalo Alto, CA 9 4 3 0 3 .
65. Ralph H. Brooks, Water Quality a n d Ecology Branch, Tennessee
V a l l e y Authority, E&D Building, Muscle S h o a l s , AL 35660.
6 6 . N. A. Brungs, U. S. Environmental Protection Agency, Environmental
Research Laboratary, Soiith Ferry Road, Narragansett, RI 02882
67-70. James H. Carpenter, RosensLiel School of Marine and Atmospheric
Science, University of Miami, 4600 Rickenbacker Causeway, Miami,
FL 3 3 1 4 9 .
71. William J. Cooper, F l o r i d a Lnternationnl University, Drinking
Water Quality Research Center, Tamiaxti Campus, Miami, FI, 3 3 1 9 9 .
7 2 . Joseph A. Cotruvo, U.S. Environmental Protection Agency, WH-550,
4 0 1 M Street, SW, Washington, D.C. 2 0 4 6 0 .
73. W. P. Davis, U.S. Environmental Protection Agency-Sabine Island,
Gulf Breeze Environmental Research Lnborat:ory, Gulf Breeze, FL
32561.
74. Max Eisenberg, Maryland State Cept . Health and Mental Hygiene,
201 W. P r e s t o n Street, Baltimore, Mn 21152.
7 5 . James A. Fava, E c o l o g i c a l A t i a l y s i s t s , Xnc-. , Ffunt ValPey/Loveton
Center, 1 5 Loveton Circle, Sparks, PID 21152.
76. A . A. G a l l i , U . S . Environmental Protection Agency, RD-682, 401 M
Street, SW, Washington, D. C. 2 0 4 6 0 .
 116

77-79. D. Heyward Hamilton, J r . , Department of Energy, EV-34, GTN,

Washington, D . C . 20545.
80. George R. H e l z , S t a n f o r d U n i v e r s i t y , Department of Geol.ogy,
S t a n f o r d CA 94305.
81. I Lyman H. Ilowe, Tennessee V a l l e y A u t h o r i t y , 150-401 B u i l d i n g ,
C h a t t a n o o g a , T N 37401
82. J . Donald Johnson, Dept. Environmental Sei-ence and E n g i n e e r i n g ,
Sc-hool of P u b l i c H e a l t h 201H, U n i v e r s i t y of North C a r o l i n a ,
Chapel H i l l , NC 27514.
83. Robert K a w a r a t a n i , E l e c t r i c Power R e s e a r c h I n s t i t u t e , 341.2
H i l l v i e w Avenue, P.O. Box 1.0412, P a l o A l t o , CA 94303.
84. Lloyd L e w i s , CE-332, Department of Energy, B i c e n t e n n i a l B u i l d i n g ,
600 E. S t r e e t , NW, Washington, D . C . 20585.
85. J a c k S. Mattice, E l e c t r i c Power R e s e a r c h I n s t i t u t e , P.O. Box
10412, P a l o A l t o , CA 94303.
86. Roger A . Minear, Radian C o r p o r a t i o n , P.O. Box 9948, Austi.n, TX
78766.
87. J . Carrel1 M o r t i s , Harvard U n i v e r s i t y , 127 P i e r c e H a l l , Cambridge,
MA 02138.
88. P h i l l . i p R. Reed, U.S. N u c l e a r K e g u l a t o r y Commission, O f f i c e of
N u c l e a r R e g u l a t o r y R e s e a r c h , Environmental. E f f e c t s , MS 1130 SS,
Washington, I1.C. 20555. >
89. J. R i c h a r d Ruane, Tennessee V a l l e y A u t h o r i t y , 248 401 B u i l d i n g ,
C h e s t n u t S t r e e t , Chattanooga, TN 37401.
90. Robert B. Samworth, U . S . N u c l e a r R e g u l a t o r y Commission, AK-5200,
Washington, D . C . 20555.
91. M a r t i n J . S t e i n d l e r (CEN-205), Argonne N a t i o n a l L a b o r a t o r y ,
9700 S. Cass Avenue, Argonne, I L 60439.
92 e Richard J. Sugam, P u b l i c S e r - v i c e E l e c t r i c & Gas Co., 60 P a r k
P l a c e , Neward, N.J 07101.
93 I J a c k T o b l e r , S c i e n c e A p p l i c a t i o a s , I n c . , B u i l d i n g C , S u i t e 100,
800 Oak Ridge T u r n p i k e , Oak Ridge, TN 37830.
94 * Caryn Woodhouse, U . S . Environmental P r o t e c t i o n Agency, Off i c e o f
Environmental Cri.l:c:ria and Assessment, C i n c i n n a t i , OH 45268.
95-121. T e c h n i c a l I n f o r m a t i o n C e n t e r , Oak Ridge, TN 37830.