Chloramine (Mono) and Nitrogen, DOC316.53.

01016

Free Ammonia
Indophenol Method1 Method 10200
0.04 to 4.50 mg/L Cl2 Powder Pillows
0.01 to 0.50 mg/L NH3–N
Scope and application: For the determination of free ammonia and monochloramine simultaneously in finished
chloraminated water. This product has not been evaluated to test for chlorine and chloramines in medical
applications in the United States.
1 U.S. Patent 6,315,950

Test preparation

Instrument specific information

Table 1 shows all of the instruments that have the program for this test. The table also
shows requirements that may vary between instruments, such as adapter and sample cell
requirements. To use this table, select an instrument, then read across to find the
corresponding information for this test.
Table 1 Instrument-specific information
Instrument Adapter Sample cell orientation Sample cell
DR 6000 A23618 The orientation key is toward the user. 4864302
DR 5000 The orientation key is toward the user.
DR 3900 LZV846 (A) The orientation key is away from the user.
DR 900 — The orientation key is toward the user.
DR 3800 LZV585 (B) The 1-cm path is aligned with the arrow on the adapter. 5940506
DR 2800
DR 2700

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.
In bright light conditions (e.g., direct sunlight), close the cell compartment on spectrophotometers, if applicable, with the
protective cover during measurements.
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.
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.

1
Items to collect
Description Quantity

Free Ammonia Reagent Solution 1 drop

Monochlor F Reagent Pillows 2
Sample cells (For information about sample cells, adapters or light shields, refer to Instrument
2
specific information on page 1.)

Refer to Consumables and replacement items 01015 for reorder information.

Sample collection and storage

Collect samples in clean glass bottles. Open the sample valve or spigot and let the water
flow for a minimum of 5 minutes. Rinse the sample bottle several times with the sample
and let the sample overflow each time, then cap the container so that there is no head
space (air) above the sample. Analyze samples immediately after collection.
Powder pillow procedure

Start

1. Start program 66, 2. Fill two sample cells to 3. Clean the 4. Insert the
Monochloramine LR. For the 10-mL line with sample. monochloramine sample monochloramine sample
information about sample Write Free Ammonia on cell. cell into the cell holder.
cells, adapters or light one sample cell. Write
shields, refer to Instrument Monochloramine on the
specific information second sample cell.
on page 1.
Note: Although the program
name may vary between
instruments, the program
number does not change.

Zero

5. Push ZERO. The display 6. Remove the sample from 7. Add the contents of one 8. Close the sample cell.
shows 0.00 mg/L Cl2. the cell holder. Monochlor F Reagent Shake the sample cell for
Powder Pillow to the sample about 20 seconds to
for monochloramine dissolve the reagent. A
measurement. green color will show if
monochloramine is present.

2 Chloramine (Mono) (4.50 mg/L) and Free Ammonia (0.50 mg/L), Indophenol Method
9. Add one drop of Free 10. Close the free 11. Start the instrument 12. When the timer expires,
Ammonia Reagent Solution ammonia sample cell. timer. A 5-minute reaction clean the monochloramine
to the sample cell for free Invert the sample cell to mix time starts. sample cell.
ammonia measurement. the reagent. For samples colder than
Close the reagent bottle to If the sample gets cloudy by 18 °C, refer to Table 2
keep the reagent stable. the end of the reaction on page 4.
period, pre-treat the sample
and do the test again. Refer
to Interferences
on page 4.

Read Start Zero

13. Insert the 14. Push READ. Results 15. Exit program 66. Start 16. Leave the
monochloramine sample show in mg/L Cl2. program 388 N, Ammonia monochloramine sample
cell into the cell holder. Free. cell in the cell holder. Push
ZERO. The display will
show 0.00 mg/L NH3–N f.

17. Remove the 18. When the reaction time 19. Close the sample cell. 20. Start the instrument
monochloramine sample cell in step 11 is complete, add Shake the sample cell for timer. A 5-minute reaction
from the cell holder. the contents of one about 20 seconds to time starts.
Monochlor F Powder Pillow dissolve the reagent. A For samples colder than
to the Free Ammonia green color will show if 18 °C, refer to Table 2
sample cell. monochloramine is present. on page 4.

Chloramine (Mono) (4.50 mg/L) and Free Ammonia (0.50 mg/L), Indophenol Method 3
 Read

21. When the timer expires, 22. Insert the free 23. Push READ. The
clean the free ammonia ammonia sample cell into results are in mg/L NH3–N f.
sample cell. the cell holder.

Color development time

Test results are strongly influenced by the sample temperature. The reaction period
indicated in the procedure is for a sample temperature of 18–20 ºC (64–68 ºF). Adjust the
reaction period according to Table 2. Samples can be read up to 15 minutes after the
listed development time.
Table 2 Color development time
Sample temperature (°C) Sample temperature (°F) Development time (mintues)
5 40 10
7 42 9
9 48 8
10 50 8
12 54 7
14 58 7
16 61 6
18 68 4
20 73 3
23 75 2.5
25 77 2
> 25 > 77 2

Interferences
This method is intended for finished, chloraminated drinking water samples that have a
measurable combined (total) chlorine disinfectant residual. Samples that do not have a
disinfectant residual and samples that have a chlorine demand may show low ammonia
test results. Blanks and ammonia standards that are analyzed without a disinfectant
residual must be prepared with high quality, reagent grade water.
The substances that are shown in Interferences on page 4 do not interfere in the free
ammonia determination at or below the given concentration.
Table 3 Non-interfering substances
Substance Maximum level tested
Aluminum 0.2 mg/L Al
Chloride 1200 mg/L Cl–
Copper 1 mg/L Cu

4 Chloramine (Mono) (4.50 mg/L) and Free Ammonia (0.50 mg/L), Indophenol Method
 Table 3 Non-interfering substances (continued)
Substance Maximum level tested
Iron 0.3 mg/L Fe
Manganese 0.05 mg/L Mn
Nitrate 10 mg/L NO3––N
Nitrite 1 mg/L NO2––N
Phosphate 2 mg/L o-PO4
Silica 100 mg/L SiO2
Sulfate 1600 ppm as SO42–
Zinc 5 ppm Zn

Samples that contain high levels of both Total Hardness and Alkalinity may become
cloudy after the addition of the Free Ammonia Reagent Solution. If this occurs by the end
of the first reaction period, the sample for Free Ammonia measurement must be
pretreated as follows:
1. Measure 10 mL of sample into the sample cell for Free Ammonia.
2. Add the contents of one Hardness Treatment Reagent Powder Pillow to the sample.
3. Tighten the cap on the sample cell and invert until the reagent is dissolved.
4. Remove the cap.
5. Use the pretreated sample in the test procedure for the Free Ammonia sample.
Note: The sample for Monochloramine measurement does not need pretreatment.

Accuracy check
Standard solution method
Items to collect:
• Buffer Powder Pillow, pH 8.3
• Nitrogen, Ammonia Standard Solution, 100-mg/L as NH3–N
• Chlorine Solution Ampules, 50–70 mg/L
• 100-mL Class A volumetric flask
• 50-mL graduated cylinder
• Pipet, TenSette®, 0.1–1.0 mL and tips
• Pipets, Volumetric, 2-mL Class A and Mohr, 5-mL
• Pipet bulb
• Organic-free water

1. Prepare a 4.5-mg/L (as Cl2) monochloramine standard immediately before use as

follows.
a. Add the contents of one Buffer Powder Pillow, pH 8.3 to approximately 50 mL of
organic-free water in a clean 100-mL Class A volumetric flask. Swirl to dissolve
the powder.
b. Use a Class A volumetric pipet to add 2.00 mL of Nitrogen, Ammonia Standard
Solution, 100-mg/L as NH3–N into the flask.
c. Dilute to the mark with organic-free water. Mix well. This is a 2.00-mg/L buffered
ammonia standard.
d. Use a graduated cylinder to add 50.00 mL of the buffered ammonia standard into
a clean 100-mL beaker. Add a stir bar.
e. Find the exact concentration of the Chlorine Solution Ampules, 50–70 mg/L from
the label on the package.
f. Calculate the volume of the Chlorine Solution to add to the ammonia standard:
mL chlorine solution required = 455/(free chlorine concentration).

Chloramine (Mono) (4.50 mg/L) and Free Ammonia (0.50 mg/L), Indophenol Method 5
 g. Open an ampule and use a glass Mohr pipet to add the calculated amount of
Chlorine Solution slowly to the ammonia standard in the beaker. Keep the beaker
on a stir-plate at medium speed during the chlorine addition.
h. Stir the monochloramine solution for 1 minute after the Chlorine Solution addition
is complete.
i. Quantitatively transfer the monochloramine solution to a clean 100-mL Class A
volumetric flask. Dilute to the mark with organic-free water and mix well. This is a
nominal 4.5-mg/L (as Cl2) monochloramine standard.
2. Use this standard within 1 hour of preparation. Use the test procedure to measure the
concentration of the monochloramine standard solution.
3. Compare the expected result to the actual result.
Note: The factory calibration can be adjusted slightly with the standard adjust option so that the
instrument shows the expected value of the standard solution. The adjusted calibration is then
used for all test results. This adjustment can increase the test accuracy when there are slight
variations in the reagents or instruments.

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:
• Ammonium Nitrogen Standard Solution, 10 mg/L NH3–N
• 50-mL mixing cylinders
• 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 0.3 mL, 0.6 mL and
1.0 mL of the standard solution, respectively, to three 50-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.

Standard solution method

Use the standard solution method to validate the test procedure, reagents and
instrument.
Items to collect:
• Ammonium Nitrogen Standard Solution, 10 mg/L NH3–N
• 100-mL plastic volumetric flask with stopper, Class A
• 2-mL volumetric pipet, Class A and pipet filler
• Deionized water—must be free of ammonia, chlorine and chlorine demand, for
example 18 MΩ-cm water from a deionizer system.

1. Prepare a 0.20 mg/L ammonia nitrogen standard solution as follows:

a. Use a pipet to add 2.00 mL of 10 mg/L ammonia nitrogen standard solution into
the volumetric flask. (Alternate preparation: add 0.4 mL of a 50 mg/L ammonia
nitrogen standard solution to the volumetric flask.)

6 Chloramine (Mono) (4.50 mg/L) and Free Ammonia (0.50 mg/L), Indophenol Method
 b. Dilute to the mark with deionized water. Mix well. Prepare this solution daily.
2. Use the test procedure to measure the concentration of the prepared standard
solution.
3. Compare the expected result to the actual result.
Note: The factory calibration can be adjusted slightly with the standard adjust option so that the
instrument shows the expected value of the standard solution. The adjusted calibration is then
used for all test results. This adjustment can increase the test accuracy when there are slight
variations in the reagents or instruments.

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
66 2.60 mg/L Cl2 2.58–2.62 mg/L Cl2 0.04 mg/L Cl2
388 0.20 mg/L NH3–N 0.19–0.21 mg/L NH3–N 0.01 mg/L NH3–N

Summary of method
Monochloramine (NH2Cl) and free ammonia (NH3 and NH4+) can exist in the same water
sample. Added hypochlorite combines with free ammonia to form more monochloramine.
In the presence of a cyanoferrate catalyst, monochloramine in the sample reacts with a
substituted phenol to form an intermediate monoimine compound. The intermediate
couples with excess substituted phenol to form a green-colored indophenol, which is
proportional to the amount of monochloramine present in the sample. Free ammonia is
determined by comparing the color intensities, with and without added hypochlorite. The
measurement wavelength is 655 nm for spectrophotometers or 610 nm for colorimeters.
Consumables and replacement items
Required reagents

Description Quantity/test Unit Item no.

Free Ammonia Reagent Set, includes: — 50/pkg 2879700

Free Ammonia Reagent Solution 1 drop 4 mL SCDB 2877336
Monochlor F Reagent Pillows 2 100/pkg 2802299

Recommended standards or Recommended standards and apparatus

Description Unit Item no.

Buffer Powder Pillow, pH 8.3 25/pkg 89868

®
Chlorine Standard Solution, 10-mL Voluette Ampule, 50-75 mg/L 16/pkg 1426810
®
Chlorine Standard Solution, 2-mL PourRite Ampule, 50-75 mg/L 20/pkg 1426820
®
Chlorine Standard Solution, 2-mL PourRite Ampules, 25–30 mg/L 20/pkg 2630020
Hardness Treatment Reagent Pillows 50/pkg 2882346
Nitrogen Ammonia Standard Solution, 10-mg/L NH3–N 500 mL 15349
®
Nitrogen Ammonia Standard Solution, 10-mL Voluette Ampule, 50-mg/L NH3–N 16/pkg 1479110
Nitrogen Ammonia Standard Solution, 100-mg/L as NH3–N 500 mL 2406549
®
PourRite Ampule Breaker, 2-mL each 2484600
®
Ampule Breaker, Voluette ampules each 2196800
Organic-free water 500 mL 2641549

Chloramine (Mono) (4.50 mg/L) and Free Ammonia (0.50 mg/L), Indophenol Method 7
Optional reagents and apparatus

Description Unit Item no.

Beaker, 100 mL, polypropylene each 108042

Beaker, glass, 100-mL each 50042H
Cylinder, mixing, 50-mL each 2088641
Flask, volumetric, Class A, 100-mL each 1457442
Free Ammonia Reagent Set 250/pkg 2879701
Monochloramine/Free Ammonia SpecCheck™ Kit each 2507500
Pipet filler, safety bulb each 1465100
®
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
Pipet, Mohr, glass, 10-mL each 2093438
Pipet, volumetric, Class A, 2-mL each 1451536
Pipet, volumetric, Class A, 50-mL each 1451541
Scissors each 2883100
Stir bar, octagonal each 2095352
Stirrer, magnetic each 2881200
Thermometer, -10 to 110 °C each 187701
Wipes, disposable 280/pkg 2097000

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