Chlorine, Free, Low Range DOC316.53.

01486

USEPA DPD Method1 Method 8021

0.02 to 2.0 mg/L Cl2 SwifTest™ Dispenser
Scope and application: For testing free chlorine (hypochlorous acid and hypochlorite ion) in water and treated
waters. USEPA accepted for reporting for drinking water analyses.2 This product has not been evaluated to test
for chlorine and chloramines in medical applications in the United States.
1 USEPA accepted for reporting wastewater and drinking water analyses.
2 Procedure is equivalent to USEPA method 330.5 for wastewater and Standard Method 4500-Cl G for drinking water.

Test preparation

Before starting
Samples must be analyzed immediately after collection and cannot be preserved for later analysis.
Always do tests in sample cells. Do not put the instrument in the sample or pour the sample into the cell holder.
Make sure that the sample cells are clean and there are no scratches where the light passes through them.
Rinse the sample cell and cap with the sample three times before the sample cell is filled.
Make sure that there are no fingerprints or liquid on the external surface of the sample cells. Wipe with a lint-free cloth before
measurement.
Cold waters can cause condensation on the sample cell or bubbles in the sample cell during color development. Examine
the sample cell for condensation or bubbles. Remove condensation with a lint-free cloth. Invert the sample cell to remove
bubbles.
Install the instrument cap over the cell holder before ZERO or READ is pushed.
Do not use the same sample cells for free and total chlorine. If trace iodide from the total chlorine reagent is carried over into
the free chlorine determination, monochloramine will interfere. It is best to use separate, dedicated sample cells for free and
total chlorine measurements.
If the test result is over-range, or if the sample temporarily turns yellow after the reagent addition, dilute the sample with a
known volume of high quality, chlorine demand-free water and do the test again. Some loss of chlorine may occur due to the
dilution. Multiply the result by the dilution factor. Additional methods are available to measure chlorine without dilution.
After the test, immediately empty and rinse the sample cell. Rinse the sample cell and cap three times with deionized water.
For the best results, measure the reagent blank value for each new lot of reagent. Replace the sample with deionized water
in the test procedure to determine the reagent blank value. Subtract the reagent blank value from the sample results.
Review the Safety Data Sheets (MSDS/SDS) for the chemicals that are used. Use the recommended personal protective
equipment.
Dispose of reacted solutions according to local, state and federal regulations. Refer to the Safety Data Sheets for disposal
information for unused reagents. Refer to the environmental, health and safety staff for your facility and/or local regulatory
agencies for further disposal information.

Items to collect
Description Quantity

SwifTest™ DPD Free Chlorine Reagent 1 dispensation

Sample cells, 25-mm (10 mL) 2

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

1
Sample collection
• Analyze the samples immediately. The samples cannot be preserved for later
analysis.
• Chlorine is a strong oxidizing agent and is unstable in natural waters. Chlorine 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. Do not use plastic containers because these
can have a large chlorine demand.
• Pretreat glass sample containers to remove chlorine demand. Soak the containers in
a weak bleach solution (1 mL commercial bleach to 1 liter of deionized water) for at
least 1 hour. Rinse fully with deionized or distilled water. If sample containers are
rinsed fully with deionized or distilled water after use, only occasional pretreatment is
necessary.
• Make 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. 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.

SwifTest™ dispenser procedure

1. Set the instrument to low 2. Prepare the blank: Fill a 3. Clean the blank sample 4. Insert the blank into the
range (LR). Refer to the sample cell to the 10-mL cell. cell holder. Point the
instrument documentation. mark with sample. Close the diamond mark on the
sample cell. sample cell toward the
keypad.

5. Install the instrument cap 6. Push ZERO. The display 7. Remove the sample cell 8. Prepare the sample: Fill
over the cell holder. shows “0.00”. from the cell holder. a second sample cell to the
10-mL mark with sample.

2 Chlorine, Free LR (0.02 to 2.00 mg/L)

9. Add one dispensation of 10. Close the sample cell. 11. Clean the prepared 12. Within 1 minute of the
DPD Free Chlorine Reagent Shake the sample cell for sample cell. reagent addition, insert the
to the second sample cell. about 20 seconds to prepared sample into the
dissolve the reagent. cell holder. Point the
Undissolved power will not diamond mark on the
affect accuracy. sample cell toward the
A pink color will show if keypad.
chlorine is in the sample.

13. Install the instrument 14. Push READ. Results

cap over the cell holder. show in mg/L Cl2.

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 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.
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 Positive interference at all levels
Chlorine Dioxide, ClO2 Positive interference at all levels
Inorganic chloramines Positive interference at all levels
Chloramines, organic May interfere
Hardness No effect at less than 1000 mg/L as CaCO3

Chlorine, Free LR (0.02 to 2.00 mg/L) 3

Interfering substance Interference level
Manganese, Oxidized Pre-treat the sample as follows:
(Mn4+, Mn7+) or Chromium,
Oxidized (Cr6+) 1. Adjust the sample pH to 6–7.
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.

Monochloramine Causes a gradual drift to higher readings. When read within 1 minute after reagent addition,
3 mg/L monochloramine causes less than a 0.1 mg/L increase in the reading.
Ozone Positive interference at all levels
Peroxides May interfere
Highly buffered samples or Can prevent the correct pH adjustment of the sample by the reagents. Sample pre-treatment
extreme sample pH may be necessary. Adjust to pH 6–7 with acid (Sulfuric Acid, 1 N) or base (Sodium Hydroxide,
1 N). Correct the test result for the dilution caused by the volume additions.

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. must be
disposed of as a hazardous waste. Dispose of reacted solutions according to local, state
and federal regulations.
Accuracy check
Standard additions method
Use the standard additions method 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, 25–30 mg/L (use mg/L on label)
• Ampule breaker
• Pipet, TenSette®, 0.1–1.0 mL and tips

1. 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.
2. 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.
3. Compare the expected result to the actual result. The expected increase in the
chlorine concentration is the Cl2 mg/L concentration from the label of the standard
solution multiplied by 0.1 mL for every 10 mL of standard solution added.

Standard solution method

If the Standard Calibration Adjust feature is used to adjust the calibration curve of the
Pocket Colorimeter II, the concentration of the chlorine standard must be between
0.50 and 1.50 mg/L chlorine for the LR procedure.
Method performance
The method performance data that follows was derived from laboratory tests that were
measured on a Pocket Colorimeter II during ideal test conditions. Users can get different
results under different test conditions.

4 Chlorine, Free LR (0.02 to 2.00 mg/L)

 Precision (95% confidence interval)
1.00 ± 0.05 mg/L Cl2

Summary of method
Chlorine can be in water as free chlorine and as combined chlorine. Both forms can be in
the same solution and can be determined together as total chlorine. Free chlorine is in a
solution as hypochlorous acid or hypochlorite ion. Combined chlorine represents a
combination of chlorine-containing compounds, including monochloramine, dichloramine,
nitrogen trichloride and other chloro derivatives. The combined chlorine oxidizes iodide
(I–) to iodine (I2). The iodine and free chlorine reacts with DPD (N,N-diethyl-p-
phenylenediamine) to form a red solution. The color intensity is proportional to the
chlorine concentration. To determine the concentration of combined chlorine, complete a
free chlorine test and a total chlorine test. Subtract the results of the free chlorine test
from the total chlorine test to get the combined chlorine concentration.
Consumables and replacement items
Required reagents

Description Quantity/test Unit Item no.

SwifTest™ DPD Free Chlorine Reagent 1 dispensations each 2802300

Required apparatus

Description Quantity/test Unit Item no.

Sample cells, 10-mL round, 25 mm x 60 mm 2 6/pkg 2427606

Recommended standards and apparatus

Description Unit Item no.

®
Chlorine Standard Solution, 2-mL PourRite Ampules, 25–30 mg/L 20/pkg 2630020
®
PourRite Ampule Breaker, 2-mL each 2484600

Optional reagents and apparatus

Description Unit Item no.

Mixing cylinder, graduated, 25-mL each 2088640

Potassium Iodide, 30-g/L 100 mL 34332
Sodium Arsenite, 5-g/L 100 mL 104732
Sodium Hydroxide Standard Solution, 1.0 N 100 mL MDB 104532
Sulfuric Acid Standard Solution, 1 N 100 mL MDB 127032
®
Pipet, TenSette , 0.1–1.0 mL each 1970001
®
Pipet tips for TenSette Pipet, 0.1–1.0 mL 50/pkg 2185696
®
Pipet tips for TenSette Pipet, 0.1–1.0 mL 1000/pkg 2185628
Paper, pH, 0–14 pH range 100/pkg 2601300
DPD Free Chlorine Reagent, 10-mL, SwifTest™ Dispenser refill vial 250 tests 2105560
SpecCheck™ Secondary Standard Kit, Chlorine DPD, 0–2.0 mg/L Set each 2635300
Water, organic-free 500 mL 2641549

Chlorine, Free LR (0.02 to 2.00 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, 2014. All rights reserved. Printed in U.S.A. 04/2014, Edition 1