Chlorine, Total DOC316.53.

01028

DPD Method1 Method 10101

0.09 to 5.00 mg/L Cl2 Test 'N Tube™ Vials
Scope and application: For testing higher levels of total (free plus combined) chlorine in drinking water, treated
wastewater, cooling water or industrial process water. This product has not been evaluated to test for chlorine and
chloramines in medical applications in the United States.
1 Adapted from Standard Methods for the Examination of Water and Wastewater.

Test preparation

Instrument specific information

The table in this section shows all of the instruments that have the program for this test.
Table 1 shows adapter and light shield requirements for the instruments that use them.
To use the table, select an instrument, then read across to find the corresponding
information for this test.
Table 1 Instrument-specific information for test tubes
Instrument Adapters Light shield
DR 6000 — —
DR 5000 — —
DR 900 4846400 Cover supplied with the instrument
DR 3900 — LZV849
DR 3800 — LZV646
DR 2800 —

Before starting
Samples must be analyzed immediately after collection and cannot be preserved for later analysis.
Install the instrument cap on the DR 900 cell holder before ZERO or READ is pushed.
DR 3900, DR 3800, DR 2800 and DR 2700: Install the light shield in Cell Compartment #2 before this test is started.
For best results, measure the reagent blank value for each new lot of reagent. Replace the sample with deionized water in
the test procedure to get the reagent blank value. Subtract the reagent blank value from the sample results automatically
with the reagent blank adjust option.
For chloramination disinfection control, use one of the available Chloramine (Mono) methods.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used and use any recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Use the Safety Data Sheets for disposal
information for unused reagents. Consult the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

Items to collect
Description Quantity

Light shield (For information about sample cells, adapters or light shields, refer to Instrument
1
specific information on page 1.)
Test 'N Tube™ DPD Total Chlorine Reagent 1
Wipes, disposable varies

1
Refer to Consumables and replacement items on page 5 for reorder information.

Sample collection
• Samples must be analyzed immediately and cannot be preserved for later analysis.
• Chlorine is a strong oxidizing agent and it is unstable in natural waters. It reacts
quickly with various inorganic compounds and more slowly with organic compounds.
Many factors, including reactant concentrations, sunlight, pH, temperature and
salinity influence the decomposition of chlorine in water.
• Collect samples in clean glass bottles. Avoid plastic containers since these may have
a large chlorine demand.
• Pre-treat glass sample containers to remove any chlorine demand. Soak the
containers in a dilute bleach solution (1 mL commercial bleach to 1 liter of deionized
water) for at least 1 hour. Rinse thoroughly with deionized or distilled water. If sample
containers are rinsed thoroughly with deionized or distilled water after use, only
occasional pre-treatment is necessary.
• Be sure to get a representative sample. If the sample is taken from a spigot or faucet,
let the water flow for at least 5 minutes. Then let the container overflow with the
sample several times and then put the cap on the sample container so that there is
no headspace (air) above the sample. If a sample cell is used, rinse the cell several
times with the sample, then carefully fill to the 10-mL mark.

DPD method for Test N' Tubes

Start

1. Start program 2. Prepare the blank: Fill 3. Clean the blank vial. 4. Insert the blank vial into
89 Chlorine F&T TNT. For an empty Test 'N Tube vial the 16-mm cell holder.
information about sample to the top of the label with
cells, adapters or light sample.
shields, refer to Instrument
specific information
on page 1.
Note: Although the program
name may vary between
instruments, the program
number does not change.

2 Chlorine, Total, DPD TNT Method (5.00 mg/L)

 Zero

5. Push ZERO. The display 6. Prepare the sample: 7. Put the cap on the vial. 8. Start the instrument
shows 0.00 mg/L Cl2. Remove the cap from a Invert to mix. timer. A 3-minute reaction
Total Chlorine DPD Test N' time starts.
Tube. Fill the vial to the top
of the label with sample.

Read

9. Clean the sample vial. 10. When the timer expires, 11. Push READ. Results
insert the prepared sample show in mg/L Cl2.
into the cell holder.

Interferences
Interfering substance Interference level
Acidity More than 150 mg/L CaCO3. The full color may not develop or the color may fade instantly.
Adjust to pH 6–7 with 1 N Sodium Hydroxide. Measure the amount to be added on a separate
sample aliquot, then add the same amount to the sample that is tested. Correct the test result for
the dilution from the volume addition.
Alkalinity More than 250 mg/L CaCO3. The full color may not develop or the color may fade instantly.
Adjust to pH 6–7 with 1 N Sulfuric Acid. Measure the amount to add on a separate sample
aliquot, then add the same amount to the sample that is tested. Correct the test result for the
dilution from the volume addition.
Bromine, Br2 Interferes at all levels
Chlorine Dioxide, ClO2 Interferes at all levels
Chloramines, organic May interfere
Hardness No effect at less than 1000 mg/L as CaCO3
Iodine, I2 Interferes at all levels
Manganese, Oxidized Pre-treat the sample as follows:
(Mn4+, Mn7+) or
Chromium, Oxidized 1. Adjust the sample pH to 6–7.
(Cr6+) 2. Add 3 drops of Potassium Iodide (30-g/L) to 10 mL of sample.
3. Mix and wait 1 minute.
4. Add 3 drops of Sodium Arsenite (5-g/L) and mix.
5. Use the test procedure to measure the concentration of the treated sample.
6. Subtract this result from the result without the treatment to obtain the correct chlorine
concentration.

Chlorine, Total, DPD TNT Method (5.00 mg/L) 3

Interfering substance Interference level
Ozone Interferes at all levels
Peroxides May interfere
Highly buffered samples Can prevent the correct pH adjustment of the sample by the reagents. Sample pretreatment may
or extreme sample pH be necessary.

Pollution prevention and waste management

If sodium arsenite was added to the sample for manganese or chromium interferences,
the reacted samples will contain arsenic and must be disposed of as a hazardous waste.
Dispose of reacted solutions according to local, state and federal regulations.
Accuracy check
Standard additions method (sample spike)
Use the standard additions method (for applicable instruments) to validate the test
procedure, reagents and instrument and to find if there is an interference in the sample.
Items to collect:
• Chlorine Standard Solution, 2-mL PourRite® Ampule, 50–75 mg/L (use mg/L on label)
• Ampule breaker
• Pipet, TenSette®, 0.1–1.0 mL and tips

1. Use the test procedure to measure the concentration of the sample, then keep the
(unspiked) sample in the instrument.
2. Go to the Standard Additions option in the instrument menu.
3. Select the values for standard concentration, sample volume and spike volumes.
4. Open the standard solution.
5. Prepare three spiked samples: use the TenSette pipet to add 0.1 mL, 0.2 mL and
0.3 mL of the standard solution, respectively, to three 10-mL portions of fresh sample.
Mix well.
6. Use the test procedure to measure the concentration of each of the spiked samples.
Start with the smallest sample spike. Measure each of the spiked samples in the
instrument.
7. Select Graph to compare the expected results to the actual results.
Note: If the actual results are significantly different from the expected results, make sure that
the sample volumes and sample spikes are measured accurately. The sample volumes and
sample spikes that are used should agree with the selections in the standard additions menu. If
the results are not within acceptable limits, the sample may contain an interference.

Method performance
The method performance data that follows was derived from laboratory tests that were
measured on a spectrophotometer during ideal test conditions. Users may get different
results under different test conditions.
Program Standard Precision (95% Confidence Interval) Sensitivity
Concentration change per 0.010 Abs change
89 2.68 mg/L Cl2 2.63–2.73 mg/L Cl2 0.03 mg/L Cl2

Summary of method
Chlorine can be present in water as free chlorine and as combined chlorine. Both forms
can exist in the same water and be determined together as total chlorine. Free chlorine is
present as hypochlorous acid and/or hypochlorite ion. Combined chlorine exists as
monochloramine, dichloramine, nitrogen trichloride and other chloro derivatives. The
combined chlorine oxidizes iodide in the reagent to iodine. The iodine and free chlorine
react with DPD (N,N-diethyl-p-phenylenediamine) to form a pink color which is
proportional to the total chlorine concentration.

4 Chlorine, Total, DPD TNT Method (5.00 mg/L)

 To find the concentration of combined chlorine, run a free chlorine test and a total
chlorine test. Subtract the results of the free chlorine test from the total chlorine test to
obtain the combined chlorine concentration. The measurement wavelength is 530 nm for
spectrophotometers or 520 nm for colorimeters.
Consumables and replacement items
Required reagents

Description Quantity/test Unit Item no.

Test 'N Tube™ DPD Total Chlorine Reagent 1 50/pkg 2105645

Recommended standards and apparatus

Description Unit Item no.

®
Chlorine Standard Solution, 2-mL PourRite Ampules, 50–75 mg/L 20/pkg 1426820
®
PourRite Ampule Breaker, 2-mL each 2484600

Optional reagents and apparatus

Description Unit Item no.

®
Pipet, TenSette , 0.1–1.0 mL each 1970001
Pipet tips for TenSette Pipet 1970001 50/pkg 2185696
Pipet tips for TenSette Pipet 1970001 1000/pkg 2185628
Paper, pH, 0–14 pH range 100/pkg 2601300
®
Ampule Breaker, Voluette ampules each 2196800
Test tube rack each 1864100
Potassium Iodide, 30 g/L 100 mL 34332
Sodium Arsenite, 5 g/L 100 mL 104732
100 mL
Sodium Hydroxide Standard Solution, 1.0 N 104532
MDB
100 mL
Sulfuric Acid Standard Solution, 1 N 127032
MDB
®
Chlorine Standard Solution, 10-mL Voluette Ampule, 50–75 mg/L 16/pkg 1426810
®
Chlorine Standard Solution, 2-mL PourRite Ampule, 25-30 mg/L 20/pkg 2630020

Chlorine, Total, DPD TNT Method (5.00 mg/L) 5

 FOR TECHNICAL ASSISTANCE, PRICE INFORMATION AND ORDERING: HACH COMPANY
In the U.S.A. – Call toll-free 800-227-4224 WORLD HEADQUARTERS
Outside the U.S.A. – Contact the HACH office or distributor serving you. Telephone: (970) 669-3050
On the Worldwide Web – www.hach.com; E-mail – techhelp@hach.com FAX: (970) 669-2932

© Hach Company/Hach Lange GmbH, 1989–2013. All rights reserved. 04/2013, Edition 8