Lab 9:

Chlorine Residual and Chlorine Demand

Reading Assignment
Read Chapters 7 and 8 in Simplified Procedures for Water Examination.
Chlorine Dose, Demand, and Residual
Most water treatment plants are required to disinfect the water, a process
used to kill harmful bacteria. The most frequently used method of
disinfection is the addition of chlorine. Here, we will briefly introduce three
terms used durin chlorination ! chlorine dose, chlorine demand, and
chlorine residual. These three characteristics are related to each other usin
the followin equation"
#Chlorine demand$ % #Chlorine dose$ ! #Chlorine residual$
The amount of chlorine added to the water is known as the chlorine dose.
This is a measured quantity chosen by the operator and introduced into the
water usin a chlorinator or hypochlorinator.
&s the chlorine reacts with bacteria and chemicals in the water, some of the
chlorine is used up. The amount of chlorine used up by reactin with
substances in the water is known as the chlorine demand. 'f nothin reacts
with the chlorine #as would be the case in distilled water$, then the chlorine
demand is (ero. Howe)er, in most cases the operator should count on some
of the chlorine dose bein used up when it reacts with substances in the
water.
The amount of chlorine remainin in the water after some of the chlorine
reacts with substances in the water is known as the chlorine residual. This
lab introduces a test which can be used to calculate the chlorine residual.
The chlorine residual is the most important of these three )alues ! dose,
demand, and residual ! because it represents the actual amount of chlorine
remainin in the water to act as a disinfectant.
The test for chlorine residual is performed frequently at most water
treatment plants. *ince reulations require a certain le)el of chlorine in
water at the far ends of the distribution system, operators should be sure to
test the chlorine residual in the distribution system as well as in the clear
well.
Introduction to Testing Procedures
The +,+ Colorimetric Method introduced in this lab is one of se)eral
procedures which can be used to test for chlorine residual. This method
requires compensation for color and turbidity and can detect chlorine
concentrations only as low as -. u as Cl
/
01. Standard Methods introduces
se)eral other procedures and e2plains which procedures are most effecti)e
under a )ariety of circumstances. 'n e)ery case, remember that chlorine is a
relati)ely )olatile substance and that samples should be tested as soon as
possible after the water is collected.
The chemistry in)ol)ed in the +,+ Colorimetric Method is relati)ely
simple. The buffer lowers the pH of the sample to 3 or less. 'n this pH
rane, chlorine in the water is able to react with the added potassium iodide,
replacin the iodine which is released into the solution as shown below"
/4' 5 Cl
/
/4Cl 5 '
/
6hen free iodine becomes present in the water, the indicator makes the
solution chane to a red color, with the intensity of the color equi)alent to
the amount of chlorine found in the solution.
Equiment
This procedure requires a piece of colorimetric equipment, some lassware,
and titration equipment. The colorimetric equipment must be one of the
followin"
*pectrophotometer, for use at a wa)elenth of 7-7 nm and
pro)idin a liht path of - cm or loner.
8ilter photometer, equipped with a filter ha)in ma2imum
transmission in the wa)elenth rane of 39. to 7:. nm and
pro)idin a liht path of - cm or loner.
Reagents
*tandard potassium permananate solutions
,hosphate buffer solution
;,;!+iethyl!p!phenylenediamine #+,+$ indicator solution
*tandard ferrous ammonium sulfate #8&*$ titrant
,otassium iodide #4'$ crystals
Chlorine!demand!free water
#8or information on how to prepare these reaents, see p. 3!</ in Standard
Methods.$
Laborator! Procedure
-. Calibrate the photometric equipment usin the followin procedure. ;ote
that this procedure uses potassium permananate solutions. =ou can use
chlorine solutions to calibrate the equipment by followin the procedure
in Standard Methods on paes 3!<: to 3!<3.
a. *et -..>T on the spectrophotometer or filter photometer usin a distilled
water blank, in accordance with manufacturer?s instructions. #,repare the
distilled water blank in the same manner as you prepare the sample for
testin.$
b. ,repare a series of potassium permananate standards co)erin the
equi)alent chlorine rane of ...7 to 3 m01. #The procedure for producin
the standards is e2plained in Standard Methods on pae 3!<3.$
c. 1abel empty flasks for each standard. ,lace 7 m1 of phosphate buffer and
7 m1 of +,+ indicator reaent in each labelled flask.
d. &dd -.. m1 of each prepared potassium permananate standard solution
to the appropriate flask and mi2 thorouhly.
e. 8ill a photometer or colorimeter cell with the solution in each flask and
read each standard at a wa)elenth of 7-7 nm.
f. 'n the data section, plot a standard cur)e of m01 equi)alent chlorine
)ersus >T.
. Return the cell contents to the appropriate flask and titrate with 8&*
titrant as a check on any absorption of permananate by distilled water.
/. Measure the chlorine content of the sample.
a. ,ipette ..7 m1 of phosphate buffer solution into an empty test tube.
b. &dd ..7 m1 of +,+ indicator solution to the test tube.
c. &dd -. m1 of sample water and read the color immediately. @se the
standard cur)e to determine the amount of chlorine in the sample. Record
this in the +ata section as Readin &.
d. Continue by addin one )ery small crystal of 4' #about ..- m$ to the test
tube and mi2in. Read the color immediately. @se the standard cur)e to
determine the amount of chlorine in the sample. Record this in the +ata
section as Readin A.
e. Continue by addin se)eral crystals of 4' #about ..- $ to the test tube
and mi2in. 1et the solution stand for about two minutes to allow color to
de)elop, then read the color. @se the standard cur)e to determine the
amount of chlorine in the sample. Record this in the +ata section as
Readin C.
f. ,lace a )ery small crystal of 4' #about ..- m$ in a clean test tube. &dd
-. m1 of the sample and mi2. 'n a separate tube, add ..7 m1 of the
phosphate buffer solution and and ..7 m1 of the +,+ indicator solution and
mi2. &dd the contents of the second tube to the first tube and mi2. Read the
color immediately. @se the standard cur)e to determine the amount of
chlorine in the sample. Record this in the +ata section as Readin ;.
:. Calculate the amount of each type of chlorine usin the calculation
methods listed in Table / in the +ata section.
For example, let's consider our calculations if the readings were A = 1!
mg"#, $ = 1% mg"#, & = '( mg"#, and ) = 1* mg"#
First, the amount of free chlorine was shown +, -eading A to +e 1! mg"#
.he amount of monochloramine is calculated as/
$ 0 A = 1% mg"# 0 1! mg"# = !% mg"#
So the concentration of monochloramine is !% mg"#
Since ) is more than !, the dichloramine concentration is calculated as/
& 0 ) = '( mg"# 0 1* mg"# = !1 mg"#
So the concentration of dichloramine is !1 mg"#
Finall,, since ) is more than ! and there are monochloramines present, the
amount of trichloramine is calculated as follows/
'2) 0 $3 = '21* mg"# 0 1% mg"#3 = 1'mg"#
So the concentration of trichloramine is 1' mg"#
Data
"tandard Cur#e
Table $
Reading
%T
mg&L chlorine
&
A
C
;
Table '
T!e of
Chlorine
Calculation (ethod mg&L
8ree Chlorine &
Monochloramine A ! &
+ichloramine 'f ;%., then C ! AB
'f ;C., then C ! ;
Trichloramine 'f ;%., then . m01B
'f ;C. and #A ! &$ % ., then /#;
! &$
'f ;C. and #A ! &$C., then /#; !
A$
)irtual Lab
There are two )irtual labs introducin other methods of chlorine residual
testin not co)ered by this pae. The first )irtual lab introduces a titration
method while the second )irtual lab introduces a field testin method which
can be used in the distribution system. There is an assinment that needs to
be completed concernin the )irtual lab, so please print the assinment first
and then answer the questions as you perform the lab. Dnce you ha)e the
assinment completed, lo in and complete the assinment online to be
entered directly into the database.
"ources
&merican ,ublic Health &ssociation, &merican 6ater 6orks &ssociation,
and 6ater En)ironment 8ederation. -998. Standard Methods for the
Examination of Water and Wastewater. &merican ,ublic Health
&ssociation, 6ashinton, +.C.
Chapter < and &ppendi2 +" Methods Checklist" +,+ Total Chlorine .
+rinkin 6ater and 6astewater Dperator 'nformation Center. ,ennsyl)ania
+epartment of En)ironmental ,rotection.