Ammonia Electrode, Model 50250 - Instruction Manual

51940-88
Ammonia Gas Sensing

Combination Electrode
Model 50250
© Hach Company, 1999. All rights reserved. Printed in the U.S.A. hm/dk 4/99 1ed
TRADEMARKS OF HACH COMPANY
2
TABLE OF CONTENTS
SPECIFICATIONS................................................................................................................. ... 5
SAFETY.................................................................................................................................... 7
SECTION 1 INTRODUCTION ........................................................................................ 9

1.1 Electrode Description.......................................................................................................... 9
1.2 Preparing the Electrode For Use ....................................................................................... 10
1.2.1 Ammonia Modules and Membranes........................................................................ 11
1.2.2 Replacing the Internal Filling Solution.................................................................... 12
1.2.3 Conditioning the Electrode ...................................................................................... 13
1.3 Checking The Ammonia Electrode Slope......................................................................... 13
1.4 Measuring Hints ................................................................................................................ 14
1.5 The Air Gap Accessory ..................................................................................................... 16
SECTION 2 APPLICATIONS (sension™2 & 4 meters) ........................................... 17

NITROGEN, AMMONIA IN WATER .................................................................................... 19
AMMONIA DISTILLATION.................................................................................................. 27
NITROGEN, AMMONIA IN WASTEWATER....................................................................... 31
NITROGEN, AMMONIA
KNOWN ADDITION METHOD ..................................................................................... 41
DIGESTION FOR LIQUIDS................................................................................................... 49
TOTAL KJELDAHL NITROGEN........................................................................................... 53
AMMONIA IN SOLUTIONS CONTAINING FATS,
FATTY ACIDS, OILS, AND SURFACTANTS................................................................. 63
SECTION 3 ANALYTICAL METHODS (mV meters) ............................................ 71

DIRECT MEASUREMENT METHOD (with Graph Paper) .................................................. 73
3.1 Preparing Standards for a Calibration Curve .................................................................... 74
ANALYSIS WITH a pH/mV METER AND CALCULATOR............................................... 83
MEASURING LOW LEVELS OF AMMONIA ..................................................................... 87
KNOWN ADDITION METHOD WITH A pH/mV METER ................................................. 91
SECTION 4 ELECTRODE MAINTENANCE ........................................................... 95

4.1 Storing the Electrode......................................................................................................... 95
4.1.1 Short-term Storage................................................................................................... 95
4.1.2 Long-term Storage ................................................................................................... 95
3
TABLE OF CONTENTS, continued
SECTION 5 ELECTRODE CHARACTERISTICS .................................................. 97

5.1 Theory of Operation.......................................................................................................... 97
5.2 Electrode Response........................................................................................................... 98
5.3 Reproducibility ................................................................................................................. 99
5.4 Temperature Effects .......................................................................................................... 99
5.5 Effect of Ionic Strength..................................................................................................... 99
5.6 Interferences.................................................................................................................... 100
5.7 Ammonium Ion............................................................................................................... 100
5.8 Partial Pressure of Ammonia .......................................................................................... 101
5.9 Electrode Life ................................................................................................................. 101
SECTION 6 TROUBLESHOOTING.......................................................................... 103

6.1 Checking pH Bulb Function ........................................................................................... 103
6.2 Decision Trees ................................................................................................................ 104
ELECTRODE SERVICE REQUEST QUESTIONNAIRE .................................................. 109

GLOSSARY.......................................................................................................................... 111
GENERAL INFORMATION....................................................................................... 113

APPENDIX CONVERSION TABLES .............................................................................. 115
HOW TO ORDER ................................................................................................................ 117
REPAIR SERVICE ............................................................................................................... 118
WARRANTY........................................................................................................................ 119
4
SPECIFICATIONS
Specifications subject to change without notice
Concentration Range*
0.06 to 17,000 mg/L NH3
0.05 to 14,000 mg/L NH3-N
3.6 x 10-6 to 1M
Temperature Range
Operating: 0 to 50 °C
Storage: -40 to 60 °C
pH Range
> pH 11; Ionic Strength Adjustor raises pH above 11
Slope
–57 ±3 mV/decade in linear concentration range
Response Time
95% response in three minute(s) or less in linear range
Ammonia Membrane Modules

Replaceable membrane modules; module life depends on
sample composition
Internal Filling Solution

Refillable
Electrode Storage
Dry in air (membrane in sealed vial), or in Ammonia Storage
Solution. See Storing the Electrode.
Electrode Resistance
<500 Megohm
Electrode Connector
BNC (twist type)
Dimensions
Electrode length: 14 cm (5.5 in.)
Electrode diameter: 1.3 cm (0.5 in.)
Cable length: 91 cm (36 in.)
* In this manual, concentrations are expressed in mg/L (ppm) NH3-N and moles/L (M).
5
6
SAFETY
7
8
SECTION 1 INTRODUCTION
1.1 Electrode Description

The Hach Ammonia Electrode measures ammonia gas or
ammonium ions in aqueous solutions that have been converted to
gas by the addition of a strong base. The electrode (Figure 1) is a
complete electrochemical cell consisting of a glass pH electrode
and a reference electrode.
Figure 1 Ammonia Gas Sensing Electrode
The gas-permeable membrane separates the sample from a thin

layer of electrolyte that is pressed between the pH bulb and the
membrane. At high pH, ammonium is converted to ammonia gas.
The gas diffuses through the membrane and causes a pH change
9
SECTION 1, continued
in the thin layer of electrolyte. The potential across the pH glass

changes as a result of the pH change and the electrode measures
the change in potential. The measured pH change is proportional
to the ammonia concentration in the solution (see SECTION 5 on
page 97).
The ammonia electrode will measure ammonia gas or ammonium

ion (converted to gas by strong base) in a variety of aqueous
samples. Applications include water, wastewater, boiler
feedwaters, fertilizers, biological samples, fish tanks, and more.
An Air Gap accessory is available for samples that may foul or
destroy the membrane (see Section 1.4 on page 14 for more
information).
1.2 Preparing the Electrode For Use

Before using a new Ammonia Electrode or an electrode that has
been stored dry, remove the protective cap from the end. Prepare
the electrode as follows:
1. Soak the inner body in Ammonia Electrode Filling Solution

for at least two hours before assembling the electrode. For
best results, soak overnight in a small diameter test tube or
within the ammonia electrode outer body.
2. Unscrew the top cap and remove the glass electrode inner
body from the electrode outer body. See Figure 2.
3. Screw an ammonia module into the end of the electrode outer

body until finger tight. See Section 1.2.1 for more
information about ammonia modules.
4. Fill the outer body with about 2.5 mL of Ammonia

Filling Solution.
5. Place the inner body into the outer body and screw on the
upper cap.
6. Shake the fully assembled electrode as if it were a

thermometer (removes bubbles).
10
Figure 2 Assembling the Electrode
1.2.1 Ammonia Modules and Membranes

The ammonia electrode is shipped with three ammonia modules.
Each module is a bonded white ammonia membrane within a
screw cap assembly.
Avoid excessive handling of the modules during assembly as this

may affect the membrane’s hydrophobic properties, causing
shorter electrode life. A module will last from one week to
several months, depending on usage and sample matrix.
11
Membrane failure will cause a shift in electrode potential, drift

and poor response. Replace the membrane module if:
1. The electrode response becomes very slow.
2. The results are not reproducible.
3. The slope becomes too low or shifts.
4. Visual inspection detects dark spots or discoloration of

the membrane.
Ammonia membranes without the end cap are also available. To

install the membrane:
1. Remove the used membrane (or membrane module) from

the electrode. Rinse with distilled water and blot dry.
2. Locate an end cap (without membrane) and put it where it

will be easy to reach.
3. Carefully separate a membrane from the others. Handle only

by the edges.
4. Peel the white membrane off the clear paper backing. Start at
one edge and lift the membrane gently off the paper.
5. Lay the membrane on top of the sensing end of the electrode.
6. Push the end cap over the membrane and electrode tip. Using
some pressure, screw the end cap onto the electrode until the
end cap is completely on. There must not be a gap between
the membrane and end cap.
1.2.2 Replacing the Internal Filling Solution

Replenish the filling solution if the electrode is left out in the air
for more than one hour. If electrode drift occurs with a relatively
new membrane module, the filling solution may need replacing.
1. Unscrew the membrane module. Pour out the filling solution.
2. Rinse the pH bulb and reference wire with deionized water

and gently blot dry.
12
3. Fill the module with new solution to the bottom of the

threads. Add enough filling solution to ensure the silver/silver
chloride reference wire is immersed.
4. Screw the membrane module onto the electrode body. Excess

filling solution will be expelled from the vent hole near the
top of the electrode.
1.2.3 Conditioning the Electrode

1.2.3.1 New or Stored Longer Than One Week
Place the assembled electrode into the Ammonia Electrode
Storage Solution for at least 60 minutes. Check the electrode’s
response following the directions in Section 1.3.
1.2.3.2 Between Samples

Place the electrode in Ammonia Electrode Storage Solution for at
least one minute. This reinitializes the electrode for the
next measurement.
1.2.3.3 Overnight and Up to One Week

Keep the electrode in 1000-ppm ammonia standard without
Ionic Strength Adjustor (ISA) or in the Ammonia Electrode
Storage Solution. Never let the membrane dry out. Hach
recommends covering the storage beaker and electrode body with
Parafilm to prevent solution evaporation.
1.2.3.4 Longer Than One Week

Unscrew the membrane and clean all parts of the cap and body in
deionized water. Re-assemble and store dry until reconditioning
for use.
1.3 Checking The Ammonia Electrode Slope

1. If using a Hach meter, select the mV mode according to the
meter’s instruction manual.
2. If using a Hach sension™2 meter, go to step 3. If using a

sension4 meter: 1) Press SETUP. Use the Up Arrow to scroll
to Stabilizing.... 2) Press ENTER. Enter a stability criteria of
0.1 mV/min., then press ENTER. 3)Press EXIT to return to
Reading mode.
13
3. Select two standards above 0.5 mg/L NH3-N that are a decade
(factor of 10) apart and fall within a concentration range that
is close to the sample concentration range.
Note: The electrode must be properly conditioned before checking
the slope.
4. Using a 25-mL graduated cylinder, measure 25 mL of each

standard into separate 50-mL plastic beakers. Add a stir bar
to each beaker.
5. Add the contents of one Ammonia Ionic Strength Adjustor

(ISA) Powder Pillow, or add 0.1 g of ISA powder, to the
50-mL beaker with the lowest ammonia concentration. Rinse
the electrode well with deionized water and blot dry.
6. Place the beaker on a magnetic stirrer and stir at a moderate

rate. The solution should turn blue.
7. Place the electrode into the beaker being stirred. When a

steady mV reading is obtained, record the potential.
8. Remove the electrode and rinse with deionized water. Blot

dry with a paper towel.
9. Prepare the higher standard as in steps 4 and 5. Immerse the

electrode in this standard.
10. Record the mV potential when it is stable.
11. Subtract the first mV reading from the second reading. The
potential should have changed –57 ±3 mV.
1.4 Measuring Hints

These hints will improve the accuracy of the calibration curve and
sample measurements.
• Two alternatives exist for handling solutions that contain oils,

sludge, waste, or surfactants. One is to digest the sample
before measurement using a total kjeldahl nitrogen (TKN)
procedure. The procedure will measure all the free NH4+ or
NH3 in the sample, as well as the nitrogen from amines
converted to NH4+ during digestion. The second choice is to
use an air gap accessory. This will only measure the free
14
NH4+ or NH3 in the sample and is not appropriate for

measuring aminated nitrogen.
• To improve response time and the reproducibility of the

electrode, immerse it in Ammonia Storage Solution for at
least 15 minutes after it is first assembled. Between samples
or standards, immerse it in the Storage Solution for 1 minute.
This re-establishes a neutral pH between the sensing glass
and the membrane before the next measurement. Rinse the
electrode with deionized water before placing it in a sample
or standard.
• Check the electrode for accuracy after every hour of use in

fresh calibration standard. Recalibrate if necessary.
• Make sure all samples and standards are at the same

temperature (within 1 °C). If a previous calibration is used, it
should have been prepared at the same temperature as the
samples being measured.
• Use a magnetic stirrer and stir bar; stir at a constant rate. This
speeds response time and permits a lower detection limit.
• For best accuracy, especially at low levels where long sample

stirring is necessary, use a Hach electromagnetic stirrer that
won’t heat the sample (see Accessories). Or, place an
insulating pad (cardboard or foam) between the sample
container and stirrer.
• Excessive mixing or stirring causes rapid diffusion of

ammonia out of the sample, making measurements
inaccurate. Do not vortex the sample.
• Add the correct amount of Ionic Strength Adjustor (ISA) to

each standard and sample so the ionic strength is constant
(see Section 5.5 on page 99).
• Measure samples and standards within 15 minutes after

adding ISA because ammonia gas can escape out of the
solution. Covering low-concentration samples and standards
with parafilm (leave a hole for the electrode) reduces
ammonia loss. The air gap accessory also minimizes
ammonia loss and prolongs membrane life.
15
• Keep stored samples in tightly capped bottles to prevent NH3

contamination from the atmosphere. Pour samples just before
measuring. Do not leave them out too long or they will
become contaminated with atmospheric NH3. Recap the
standards immediately.
1.5 The Air Gap Accessory

The Ammonia Electrode uses a fine, porous membrane to
separate the sample solution from a thin layer of electrolyte that
coats the pH sensing bulb inside the electrode. In a closed system
saturated with water vapor, the ammonia electrode reacts to
ammonia in the gas phase. Measurements of solutions above
10- 3 M (14 mg/L) ammonia are possible under these conditions.
Ammonia gas diffuses through the air space between the
membrane and solution, then through the membrane. The air
space has slightly different diffusion characteristics than the
membrane, which increases the response time.
The membrane of the ammonia electrode is gas-permeable and

hydrophobic. Liquid water does not wet it or penetrate the pores.
If a sample solution is nonaqueous, or if it contains a surfactant
which wets the membrane, the liquid penetrates the membrane.
This causes difficulties in samples such as sewage, which
contains surfactants, and samples which are nonaqueous, such as
latex paint or nylon. To measure ammonia in such samples, use
the Air Gap Accessory, which suspends the electrode above the
sample and provides a closed system.
The Air Gap Accessory optimizes performance and extends the

usable lifetime of the membrane module. Samples containing
substances known to cause membrane failure (e.g., surfactants,
oils, fats) can be measured repeatedly with this accessory. Slopes,
absolute mV readings, and response times may change
significantly when the Air Gap Accessory is used. Therefore,
both calibrations and measurements should be made with the
Air Gap Accessory.
16
SECTION 2 APPLICATIONS (sension™2 & 4 meters)
17
18
Method 10000
NITROGEN, AMMONIA IN WATER (0.1 to 1000 mg/L NH3-N)
Using a Hach sension™ Meter
10 mg/L
100mg/L
1. Prepare the electrode 2. Rinse the electrode 3. For calibration, use 4. After conditioning,
as described in Section and place it in the two ammonia standards connect the Ammonia
1.2 on page 10. Ammonia ISE Storage of 10 and 100 mg/L ISE to the pH/ISE meter.
Solution with the NH3-N. For more Verify that BNC is
module on to condition accurate analysis, selected in Setup 1 of the
for at least 15 minutes. bracket the expected Setup menu.
sample concentration
Note: Before removing the Note: One BNC and one
electrode from the storage with two standards that five-pin connector are on
solution, the reading on are one decade apart in the back of the meter.
the meter should be below concentration. Choose the BNC for the
0.1 mg/L. This insures the ammonia electrode.
electrode is properly
conditioned. After every
hour of continuous use,
place the electrode in the
storage solution for
10 minutes to thoroughly
recondition. Check with a
10 mg/L NH3-N standard
for accuracy and
recalibrate if necessary.
19
NITROGEN, AMMONIA IN WATER, continued
Standard 1
5. Press ISE/mV until 6. Press CAL. The 7. The display will 8. If necessary, use the
the display shows mg/L display will show CAL, show Standard 1 ? and number keys to change
or other selected ?, mg/L, and the active _ _ _ _ or the value of the value to match the
concentration units. keys. The units will be standard 1 from the concentration of the
flashing. Use the arrow previous calibration. standard. Do not press
keys to select the desired ENTER yet.
units, then press ENTER.
Stabilizing...
9. Transfer 25 mL of 10. Remove the 11. Add the contents of 12. Stabilizing... will
the 10-mg/L NH3-N electrode from the one Ammonia Ionic be displayed until the
standard to a 50-mL storage solution. Rinse it Strength Adjustor reading is stable.
beaker. Add a stir bar to with deionized water Powder Pillow to the
the beaker. Place the and blot dry. Place it into standard and
beaker on a magnetic the 10-mg/L NH3-N immediately press
stirrer and stir at a standard. ENTER.
moderate rate.
Note: Be sure no air Note: At high pH,
bubbles are trapped under ammonia solutions lose
the tip of the electrode. ammonia to the
atmosphere, lowering the
concentration. It is
important to take
measurements as soon as
possible after the solution
is basic.
20
Repeat steps
8–14
Standard 2
13. The display will 14. Remove the 15. Repeat steps 8-14 16. The display will
show Standard 2 ? and electrode from the for each standard. After show Store?. Press
_ _ _ _ or the value of standard. Rinse with the last standard is ENTER to store the
standard 2 from the deionized water and blot measured, press EXIT. calibration or EXIT to
previous calibration. dry. Place in storage leave the calibration
solution for one minute. mode without storing the
calibration values.
-58.0
17. Press REVIEW. Use 18. Be sure the slope 19. Transfer 25 mL of 20. Remove the
the Up arrow key to displayed is within the the sample to a 50-mL electrode from the
scroll to the last slope range recommended in beaker. Add a stir bar to storage solution. Rinse it
value. It should be the electrode manual. the beaker. Place the with deionized water
-57 ±3 mV/decade. beaker on a magnetic and blot dry. Place it into
Press EXIT to return to stirrer and stir at a the sample.
the measurement mode. moderate rate.
Note: If the slope does not
approximate -57 ±3
mV/decade, recalibration
may be necessary. If the
slope is still incorrect after
recalibration, replace the
ammonia module.
21
Stabilizing...
21. Add the contents of 22. The display will 23. Remove the
one Ammonia Ionic show Stabilizing... until electrode from the
Strength Adjustor the reading is stable. sample. Rinse it with
Powder Pillow to the Record or store the deionized water and blot
sample. measurement value. it dry. Place it in the
storage solution for at
least one minute.
Repeat steps 19-23 for
each sample.
22
Sampling and Storage

Collect samples in glass or plastic containers of convenient size.
Clean new bottles by washing with deionized or distilled water.
Fill the sample bottle completely and stopper immediately.
Analyze the sample as soon as possible.
Ammonia may be lost more quickly when sample

temperatures are above 50 °C, so it is important to collect
samples at less than 40 °C, or use a cooling coil between the
bottle and sampling point.
If chlorine is present, treat the sample immediately with sodium

thiosulfate. Add one drop of 0.1 N Sodium Thiosulfate Standard
Solution for each 0.3 mg of chlorine present in a one liter sample.
If prompt analysis is not possible, preserve the sample with

0.8 mL of concentrated sulfuric acid per liter. Use a sension pH
meter to be sure the pH of the preserved sample is between 1.5
and 2. Some wastewater samples may require more sulfuric acid
to achieve this pH. Store the sample at 4 °C. Samples preserved in
this manner may be stored up to 28 days.
Before analysis, neutralize the sample to pH 7 with 5 N sodium

hydroxide. Do not let the pH go above 10. Correct the test results
for the volume addition.
Do not use mercuric chloride as a preservative because ammonia

complexes with mercuric ions.
Accuracy Check
To verify measurement accuracy, run a standard addition spike on
the sample. This provides more complete information about
possible inaccuracies, because the measurement includes any
interferences that may be present in the actual sample.
The spike should roughly double the measured concentration

without significantly diluting the sample. To run a standard
addition sample, use Table 1 to determine the concentration and
volume of standard to spike your sample. It is important to
accurately transfer the volume of original sample. Simply add the
amount and concentration specified in Table 1 to the sample and
record the reading when it is stable. Do not allow the sample to
23
stand too long before spiking, as ammonia will be lost to the

atmosphere. Then proceed with the calculations. Generally,
results from 90-110% recovery are considered acceptable.
Table 1 Spiking volumes
Measured
Measured Standard
Sample Standard
Sample Concentration
Concentration Volume (mL)
Volume (mL) (mg/L)
(mg/L)
0.1–0.6 25 100 0.1
0.6–1.0 25 100 0.2
1.0–1.5 25 100 0.3
1.5–3.0 25 100 0.5
3–6 25 100 1.0
6–10 25 100 2.0
10–15 25 100 3.0
15–25 25 1000 0.5
25–35 25 1000 0.7
35–50 25 1000 1.0
50–100 25 1000 2.0
Calculate percent recovery as follows:

100 ( X s – Xu )
% Recovery = ---------------------------------
-
K
Where:
Xs = measured value for spiked sample in mg/L
Xu = measured value for unspiked sample adjusted for dilution by the
spike, in mg/L
K = known value of the spike in the sample in mg/L
Calculations:
i X ×V u
1. X u = -----------------
-
Vu + V
Where:
Xi = measured value of unspiked sample in mg/L
Vu = volume of separate unspiked portion in mL
V = volume of spike in mL
24
C×V
2. K = ----------------
-
Vu + V
Where:
C = concentration of standard used in spike in mg/L
Vu = volume of separate portion before spike in mL
3. Final calculation using Xu and K:

100 ( X s – Xu )
% Recovery = ---------------------------------
-
K
Example: A sample was analyzed and read 5.0 mg/L NH3-N. As

directed in Table 1, a 1.0-mL spike of 100-mg/L NH3-N standard
was added to the 25-mL sample, giving a result of 8.75 mg/L.
Calculate the percent recovery as follows:

mg/L × 25 mL
1. X u = 5.0
---------------------------------------------- = 4.81 mg/L
25 mL + 1 mL
2. K = 100 mg/L × 1 mL- = 3.85 mg/L

-------------------------------------------
25 mL + 1 mL
100 × ( Xs – X u ) × ( 8.75 – 4.81 -) = 102.3 % Recovery
3. - = 100
%R = --------------------------------------- -------------------------------------------------
K 3.85
Method Performance
Precision
In a single lab using a standard solution of 5.0 mg/L and two
electrodes with a single sension2 meter, a single operator
obtained a standard deviation of 0.095 mg/L ammonia nitrogen.
Each electrode was exposed to seven test solutions and the meter
default stability criteria was 0.5 mV/min. Between test solutions,
electrodes were rinsed and placed in the storage solution until a
reading of <0.1 mg/L was obtained.
Interferences
Low molecular weight, volatile amines cause a
positive interference.
Mercury and silver interfere by complexing with ammonia.
25
High concentrations of dissolved ions affect the measurement.

For calibration use standard solutions that have about the same
total concentration of dissolved species as the sample.
REQUIRED REAGENTS
Quantity Required
Description Per Test Unit Cat. No.
Ammonia Electrode Filling Solution, 60 mL ......................3 mL........... 5/pkg.......... 50287-05
Ammonia Electrode Storage Solution .................................1 mL........ 500 mL .......... 25412-49
Ammonia Ionic Strength Adjustor Powder Pillows................ 1 .......... 100/pkg .......... 44471-69
Ammonia (Nitrogen) Standard Solutions:
10 mg/L NH3-N...............................................................25 mL....... 500 mL .............. 153-49
100 mg/L NH3-N.............................................................25 mL....... 500 mL .......... 24065-49
Water, deionized.................................................................100 mL..............4 L .............. 272-56
REQUIRED APPARATUS
Ammonia Electrode, BNC...................................................... 1 .................each .......... 50250-00
Beaker, 50 mL, polypropylene................................................ 1 .................each ............ 1080-41
Bottle, wash ............................................................................ 1 ........... 500 mL .............. 620-11
sension™2 Portable pH/ISE Meter........................................ 1 .................each .......... 51725-00
sension™4 Laboratory pH/ISE Meter ...................................1 .................each .......... 51775-00
Stir Bar, 22.2 x 4.76 mm......................................................... 1 .................each .......... 45315-00
Select one based on available voltage:
Stirrer, electromagnetic, 115 V, with stand and stir bar.......... 1 .................each .......... 45300-01
OPTIONAL REAGENTS
Sulfuric Acid, concentrated ...................................................................500 mL.............. 979-49
OPTIONAL APPARATUS
Air Gap Assembly ......................................................................................each .......... 50253-00
Ammonia Electrode Membrane Modules................................................ 3/pkg.......... 50251-00
Cylinder, graduated, glass......................................................................100 mL.............. 508-42
Electrode Washer ........................................................................................each .......... 27047-00
26
Method 10008
AMMONIA DISTILLATION
Sample distillation eliminates:
• interferences from high-molecular-weight amines
• substances that could decrease membrane lifetime
• variations in ionic strength in different samples.
Distilling may be used instead of the Air Gap Accessory in

samples that contain detergents or oils. Distillation may be
required for ISE analysis if reporting to the EPA is necessary (see
USEPA accepted methods). This procedure is an adaptation of the
distillation procedure written in the 17th edition of Standard
Methods for the Examination of Water and Wastewater. The
reagent volumes have been reduced by half in the adapted
method. For the distillation, a borosilicate apparatus, such as the
Hach Distillation Apparatus (Cat. No. 22653-00), must be used.
PROCEDURE
1. Assemble the 2. Add 250 mL of 3. Using a pH 4. Pour the solution

distillation apparatus ammonia-free water and electrode and meter, into the distillation flask.
according to the 10 mL of borate buffer measure the pH of the Add a stir bar.
distillation apparatus to a 400-mL beaker. solution. Adjust the pH
manual. to 9.5 with 6 N sodium
hydroxide (NaOH).
27
AMMONIA DISTILLATION, continued
Heat control: 10 OFF
5. Turn the heater on 6. Turn the heater off 7. Collect 250 mL of 8. Using the pH
and set the control to 10. when done steaming. sample in a 250-mL electrode, neutralize the
Heat the flask and steam graduated mixing sample in the cylinder to
out the apparatus until cylinder. Add 0.5 mL of pH 7 with 1 N sodium
the distillate shows no dechlorinating agent for hydroxide or 1 N
traces of ammonia every mg/L Cl2, if sulfuric acid.
(check with ammonia necessary. Stopper and
Note: Periodically stopper
ISE to ensure ammonia invert to mix. and invert the cylinder
is gone). several times to ensure
Note: For proof of
accuracy, use a 1.0 mg/L complete mixing.
ammonia nitrogen
standard (see Optional
Reagents) in place of the
sample.
9. Measure 12.5 mL of 10. Using the pH 11. Transfer sample to 12. Measure 25 mL of
borate buffer in a electrode, adjust the pH distillation flask using 0.04 N sulfuric acid into
graduated cylinder. Add of the solution to 9.5 by a funnel. Place a stir bar a graduated cylinder.
the measured buffer to slowly adding 6 N in the flask. Pour this into a 250-mL
the solution in the sodium hydroxide. Erlenmeyer receiving
cylinder. flask (comes with the
Note: Periodically stopper
and invert the cylinder distillation apparatus).
several times to ensure
complete mixing.
28
13. Turn the water to 14. Distill until at least 15. Lower the 16. Place a 100-mL
the condenser on. Place 100 mL of distillate is receiving flask away beaker under the
the receiving flask so the collected or until there is from the delivery tube. delivery tube. Continue
tip of the delivery tube is at least 125 mL total Immediately cover the to distill for 1–2 minutes
below the surface of the volume in the receiving flask with parafilm or a to clean the dispenser
sulfuric acid. flask. stopper to prevent and delivery tube. Then
Note: For the Hach
ammonia contamination. turn the heater off.
Distillation Apparatus, set
the heat control to 10 and
the stir control to 5.
Ready
for
analysis
17. Using a pH 18. Transfer the 19. Proceed with the

electrode, adjust the pH distillate into a clean appropriate ammonia
of the distillate to pH 7 250-mL volumetric ISE analysis. Dilution is
by dropwise addition of flask. Rinse the not necessary because
1 N sodium hydroxide. Erlenmeyer receiving 250 mL of sample was
flask with ammonia-free collected originally.
water and add rinsings to
the volumetric flask.
Dilute to the mark with
ammonia-free water.
29
REQUIRED REAGENTS
Quantity Required
Borate Buffer Solution................................................22.5 mL...........1000 mL .......... 14709-53
Sodium Hydroxide, 6 N ................................................varies .......................1L .......... 23324-53
Sodium Hydroxide, 1 N ................................................varies . .100 mL MDB* ............ 1045-32
Sodium Thiosulfate, pentahydrate, ACS......................0.5 mL ................. 454 g .............. 460-01
Sulfuric Acid, 1 N.........................................................varies .............1000 mL ............ 1270-53
Sulfuric Acid, 0.04 N................................................... 50 mL ..............500 mL.......... 23393-49
REQUIRED APPARATUS
Beaker, 400 mL................................................................ 1........................each .............. 500-48
Cylinder, graduated, mixing, 250 mL .............................. 1........................each .......... 20886-46
Distillation Apparatus, General Purpose ......................... 1........................each .......... 22653-00
Flask, volumetric, 250-mL, Nalge ................................... 1........................each .......... 14060-46
Funnel, Nalge................................................................... 1........................each ............ 1083-67
OPTIONAL REAGENTS
Nitrogen, Ammonia Standard Solution, 1.0 mg/L as N.........................500 mL............ 1891-49
OPTIONAL APPARATUS
Platinum Series pH Electrode, for use with sension™ meters, 5-pin ........each .......... 51910-00
sension™2 Portable pH Meter...................................................................each .......... 51725-00
sension™3 Laboratory pH Meter ..............................................................each .......... 51750-00
sension™4 Laboratory pH/ISE Meter .......................................................each .......... 51775-00
* Marked Dropper cBottle
30
Method 10001
NITROGEN, AMMONIA IN WASTEWATER (0.1–10 mg/L NH3-N)
USPEA accepted for reporting*
Calibration
Prepare ammonia standard working solutions of 10.0, 1.0 and
0.1 mg/L ammonia nitrogen from a 100-mg/L stock solution.
Prepare the standards daily before use. Higher or lower
concentration ranges (0.05–1400 mg/L NH3-N) can be obtained
by calibrating the meter with different standard solutions.
PROCEDURE
1. Assemble the 2. Rinse the electrode 3. During the 4. Prepare a 1.0-mg/L

electrode as described in with deionized water. conditioning period NH3-N standard by
Section 1.2 on page 10. Place it in the Ammonia prepare three standards. pipeting 25 mL of the
ISE storage solution Make a 10-mg/L NH3-N 10-mg/L standard into a
with the module on to standard by pipeting 250-mL volumetric
condition for at least 25 mL of 100-mg/L flask. Dilute to the mark
15 minutes. NH3-N Standard into a with ammonia-free
250-mL volumetric deionized water.
Note: Before removing the
electrode from the storage flask. Dilute to the mark
solution, the reading on with ammonia -free
the meter should be below deionized water.
0.1 mg/L. This insures the
for accuracy and
* Manual distillation is not required if comparability data on representative samples in company files
show the distillation is not necessary. Manual distillation will be required to resolve any controversies.
31
NITROGEN, AMMONIA IN WASTEWATER, continued
5. Prepare a 0.1-mg/L 6. Connect the 7. Turn the meter on. 8. Press CAL. The
NH3-N standard by Ammonia ISE to the Press ISE/mV until the display will show CAL,
pipeting 25 mL of the pH/ISE meter. Verify display shows mg/L or ?, mg/L, and the active
1.0-mg/L NH3-N that BNC is selected in other chosen keys. The units will be
standard into a 250-mL Setup 1 of the Setup concentration units. flashing. Use the arrow
volumetric flask. Dilute menu. keys to select the desired
to the mark with units, then press ENTER.
Note: One BNC and one
ammonia -free deionized five-pin connector are on
water. the back of the meter.
Choose the BNC for the
ammonia electrode.
9. Transfer 100 mL of 10. Remove the 11. Pipet 2.0 mL of 12. The display will
the 0.1-mg/L NH3-N electrode from the Ammonia ISA Solution show Standard 1? and
standard to a 150-mL storage solution. Rinse it into the standard. the value from the
beaker. Add a stir bar to with deionized water Immediately proceed to previous calibration.
the beaker. Place the and blot dry. Place the the next step. Press ENTER to accept
beaker on a magnetic electrode into the the numerical value or
stirrer and stir at a 0.1-mg/L NH3-N use the number keys to
moderate rate. standard. change the value to
match the concentration
Note: Placing the Note: Be sure no air
electrode back into the bubbles are trapped under of the standard, then
storage solution prepares the tip of the electrode. press ENTER.
it for the next standard.
Leave it in the storage
solution for at least one
minute before proceeding
to the next standard.
32
Repeat steps
Stabilizing... 9–14
13. Stabilizing... will 14. Rinse the electrode 15. After the last 16. The display will
be displayed until the with deionized water. standard is measured, show Store?. Press
reading is stable. The Place it in the storage press EXIT. ENTER to store the
display will show solution for one minute. calibration or EXIT to
Standard 2 and _ _ _ _ Repeat steps 9-14 for the leave the calibration
or the value of standard 1.0- and 10-mg/L mode without storing the
2 from the previous standards. calibration values.
calibration.
17. Press REVIEW. Use 18. Remove the 19. Transfer 100 mL of 20. Remove the
the Up arrow key to electrode from the last sample to a 150-mL electrode from the
scroll to the second standard. Rinse it with beaker. Add a stir bar to storage solution. Rinse it
slope value. It should be deionized water, and the beaker. Place the with deionized water
-57 ±3 mV/decade. place it in the storage beaker on a magnetic and blot dry. Place it into
Press EXIT to return to solution. stirrer and stir at a the sample.
measurement mode. moderate rate.
Note: If the slope is not -
57 ±3 mV/decade,
recalibration may be
necessary. If the slope is
still incorrect after
ammonia module.
33
Repeat steps
18–22
21. Pipet 2.0 mL of 22. Stabilizing... will Note: For the distillation
Ammonia ISA solution be displayed until the procedure in this manual,
into the sample and reading is stable. Record the capture volume after
distillation and the sample
proceed immediately to or store the
volume before distillation
the next step. measurement value. is 250 mL, so the
Note: At high pH, Repeat steps 18–22 for concentration from this
ammonia solutions lose step is the actual
other samples.
ammonia to the concentration.
atmosphere, lowering the Note: Stabilization will
take about 1 to 2 minutes Note: After every hour of
concentration. It is
for concentrations above continuous use the
important to take
1.0 mg/L NH3-N and electrode should be
longer for lower placed in the storage
concentrations. Slow solution for a 10 minute
is basic.
downward drift in period for thorough
Note: For most concentration indicates reconditioning. Check with
wastewater samples, 1 mL probable loss of ammonia a 10 mg/L NH3-N standard
of 10 N NaOH (or to the atmosphere. for accuracy and
equivalent ISA) is Record the highest value recalibrate if necessary.
sufficient to increase the that is stable.
pH above 11. If in doubt,
check the pH with pH
paper (Cat. No. 385-33)
and add additional NaOH
in 0.1 mL increments until
the pH exceeds 11.
34

Ammonia may be lost from samples at temperatures above 50 °C,

so it is important to collect samples at less than 40 °C, or use a
cooling coil between the bottle and sampling point if necessary.


0.8 mL of concentrated sulfuric acid per liter. Use a sension™
pH meter to be sure the pH of the preserved sample is between
1.5 and 2. Some wastewater samples may require more sulfuric
acid to achieve this pH. Store the sample at 4 °C. Samples
preserved in this manner may be stored up to 28 days.

Do not use mercuric chloride as a preservative because ammonia

Accuracy
interferences that may be present in the actual sample. The spike
should roughly double the measured concentration without
significantly diluting the sample.
To run a standard addition sample, use Table 2 to prepare a spiked

sample for analysis based on the measured sample concentration.
To prepare the spiked sample, add 100 mL of the sample and the
appropriate volume and concentration of standard to the
distillation flask. Then proceed through the analysis, including
35
the distillation. Generally, results from 90–110% recovery are

considered acceptable.
Note: If distillation was not required, and you want to run a standard
addition, the following calculations are not correct. Use the
calculations following Table 1 on page 24.
Table 2 Spiking volumes
Measured
Measured Standard
Sample Standard
Sample Concentration
Concentration Volume (mL)
Volume (mL) (mg/L)
(mg/L)
0.1–0.3 100 100 0.2
0.3–0.5 100 100 0.4
0.5–0.7 100 100 0.6
0.7–0.9 100 100 0.8
0.9–1.1 100 100 1.0
1.0–3.0 100 100 2.0
3.0–6.0 100 100 4.0

100 ( X s – Xu )
% Recovery = ---------------------------------
-
K
Where:
Xs = measured value for spiked sample in mg/L (step 22)
spike, in mg/L (step 22)
Calculations:
i X ×V u
1. X u = -----------------
-
Vu + V
Where:
Xi = measured value for spiked sample in mg/L
Xu = volume of separate unspiked portion in mL
36
C×V
2. K = ----------------
-
Vu + V
Where:
Vu = volume of separate distillate (100 mL)
3. Final calculation plugging in Xu and K:

100 ( X s – Xu )
% Recovery = ---------------------------------
-
K
Example:
A 100-mL wastewater sample was analyzed and read 5.0 mg/L
NH3-N. As directed in Table 2, a 4.0-mL spike of 100-mg/L
NH3-N standard was added to the 100-mL sample, giving a final
reading of 8.75 mg/L.

mg/L × 100
1. X u = 5.0
--------------------------------------- = 4.8 mg/L
100 + 4
mg/L × 4 mL
2. K = 100
--------------------------------------------- = 3.85 mg/L
104 mL
100 × ( Xs – X u ) 100 × ( 8.75 – 4.80 )

3. %R = ---------------------------------------
- = -------------------------------------------------- = 103% Recovery
K 3.85
Method Performance
Precision
electrodes with a single sension™2 meter, a single operator
Each electrode was exposed to seven test solutions and a default
stability criteria was 0.5 mV/min. Between test solutions, the
electrodes were rinsed and placed in the storage solution until a
reading of <0.1 ppm was obtained.
Interferences
Low molecular weight, volatile amines give a positive
interference. Mercury and silver interfere by complexing with
ammonia. Distillation prior to ammonia analysis removes all
inorganic interferences, which complex ammonia.
37
Comparison Table of USEPA and Hach Method

Feature EPA Method 350.3 Hach Method 10001
Range 0.03–1400 mg/L NH3-N 0.05–1400 mg/L NH3-N
Preservation 2 mL H2SO4/L, 4 °C, 28 days 2 mL H2SO4/L, 4 °C, 28 days
Stock Solution(s) 1000 mg/L NH3-N 1000 mg/L NH3-N, 100 mg/L NH3-N
Standard Solution(s) 10 mg/L NH3-N 10 mg/L NH3-N, 1 mg/L NH3-N,
0.1 mg/L NH3-N
Sample Size 100 mL 100 mL
NaOH Used 1 mL 10 N 1 mL 10 N
pH Note pH of solution after NaOH pH of solution after NaOH addition must
addition must be >11 be >11
NaOH Caution Do not add NaOH before Do not add NaOH before immersing the
immersing the electrode electrode
Electrode Hydrophobic gas permeable Hydrophobic gas permeable membrane
membrane
Electrode Internal Ammonium Chloride Ammonium Chloride
Solution
Electrometer pH meter with expanded mV pH meter with expanded mV scale of
scale of specific ion meter specific ion meter
38
REQUIRED REAGENTS
Quantity Required
Ammonia Electrode Filling Solution, 60 mL...................... drops ........... 5/pkg ..........50287-05
Ammonia Electrode Storage Solution................................ 20 mL ...... 500 mL ..........25412-49
Ammonia Nitrogen Standard Sol’n, 100 mg/L NH3-N .... 100 mL ..... 500 mL ..........24065-49
Water, deionized ................................................................ 100 mL ............ 4 L ..............272-56
REQUIRED APPARATUS
Ammonia Electrode, combination, BNC ............................... 1................. each ..........50250-00
Beaker, 150 mL, polypropylene ............................................. 1................. each ............1080-44
Bottle, wash............................................................................ 1........... 500 mL ..............620-11
Flask, volumetric, Class A, 250 mL....................................... 1................. each ..........14574-46
Pipet, volumetric, Class A, 25.00 mL .................................... 2................. each ..........14515-40
Pipet, TenSette®, 1.0-10.0 mL ............................................... 1................. each ..........19700-10
sension™4 Laboratory pH/ISE Meter................................... 1................. each ..........51775-00
Stir Bar, 22.2 x 4.76 mm (7/16 x 3/16 in.) ................................ 1................. each ..........45315-00
Stirrer, electromagnetic, 115 V, with stand and stir bar ......... 1................. each ..........45300-01
OPTIONAL REAGENTS
Ammonia Nitrogen Standard Solution, 1000 mg/L NH3-N.......................... 1L ..........23541-53
pH Paper, 9.0–12.0 pH units ............................................................ 5 rolls/pkg ..............385-33
Sulfuric Acid, concentrated................................................................... 500 mL ..............979-49
OPTIONAL APPARATUS
Air Gap Assembly...................................................................................... each ..........50253-00
Ammonia Electrode Membrane Modules ................................................ 4/pkg ..........44475-00
Cylinder, graduated, glass ..................................................................... 100 mL ..............508-42
Electrode Washer........................................................................................ each ..........27047-00
Pipet tips for 19700-01 TenSette Pipet....................................................50/pkg ..........21856-96
Pipet tips for 19700-10 TenSette Pipet....................................................50/pkg ..........21997-96
Pipet, Volumetric, Class A, 1.00 mL.......................................................... each ..........14515-35
sension™2 Portable pH/ISE Meter ........................................................... each ..........51725-00
TenSette® Pipet, 0.1-1.0 mL ...................................................................... each ..........19700-01
39
40
Method 10002
NITROGEN, AMMONIA
KNOWN ADDITION METHOD (≥0.8 mg/L NH3-N) For Wastewater
Standard Method 4500-NH3G
USEPA Accepted for reporting wastewater analyses (with distillation)*
Because an accurate measurement requires that the concentration
approximately double as a result of the addition, the approximate
sample concentration must be known within a factor of three.
Use Table 3 to determine how to dilute a 1000 mg/L NH3-N stock

solution to use as a spiking solution. Pipet the appropriate amount
of 1000-mg/L NH3-N standard into a 100-mL volumetric flask
and dilute to the mark with ammonia-free water.
Make the spiking solution before beginning the procedure.

Known addition is also a convenient check on the results of
direct measurement.
Table 3 Making Spiking Solutions
Expected Sample
mL of 1000-mg/L Standard
Concentration
NH3-N Concentration
(mg/L)
0.8–4.0 2 20 mg/L
2.5–7.5 5 50 mg/L
5–15 10 100 mg/L
12–50 25 250 mg/L
25–75 50 500 mg/L
50–150 100 1000 mg/L
Slope Determination
Determine the slope before performing standard additions of the
sample. Use the 100 mg/L and 1000-mg/L NH3-N stock solutions
to determine the slope. Check the electrode occasionally to
determine if it is functioning properly and to determine its exact
slope value. The frequency of this operation depends on the
harshness of your sample.
* Manual distillation is not required if comparability data on representative samples in company files
show the distillation is not necessary. Manual distillation will be required to resolve any controversies.
41
NITROGEN, AMMONIA KNOWN ADDITION METHOD, continued
1. Prepare the electrode 2. Rinse the electrode 3. Connect the 4. Accurately transfer
as described in Section and place it in the Ammonia ISE to the 100 mL of NH3-N free
1.2 on page 10. Ammonia ISE Storage pH/ISE meter. Verify deionized water to a
Solution to condition for that BNC is selected in 150-mL beaker using a
Note: Only the Hach
sension 4 can perform at least 15 minutes.
™ Setup 1 of the Setup volumetric pipet or
Standard Additions. menu. graduated cylinder. Add
electrode from the storage a stir bar to the beaker.
Note: Two BNC and two
solution, the reading on five-pin connectors are on Place the beaker on a
the meter should be below the back of the meter. magnetic stirrer and stir
0.1 mg/L. This insures the Choose a BNC for the at a moderate rate.
electrode is properly ammonia electrode.
conditioned. After every Note: Stirring at a
hour of continuous use, constant, moderately fast
place the electrode in the rate speeds response and
storage solution for 10 improves accuracy.
minutes to thoroughly
for accuracy and
42
5. Pipet 1.0 mL of 6. Remove the 7. Turn the meter on. 8. The display will
10 N NaOH solution electrode from the Press STD ADDN. Press show Slope and the
into the sample. storage solution. Rinse it the arrow keys until the slope value for the last
with deionized water display shows the calibration (default is
Note: The 10-mL Hach
TenSette Pipet works and blot dry. Place the desired units. –59.2 mV). Press
conveniently for this electrode in the sample. Press ENTER. ENTER to accept the
addition, as well as the numerical value or use
Note: Be sure no air
remainder of the additions the number keys to
bubbles are trapped under
in this procedure. change the slope value.
the tip of the electrode.
Remove bubbles by lightly Press ENTER to accept
tapping the electrode or by the new value.
tilting the electrode to 20°.
mL, Sample, ? Stabilizing... Standard, ?
9. The meter will 10. The display will 11. Use the number 12. The display will
prompt for the sample show Stabilizing... until keys to enter the volume show Standard, ?, and
volume (in mL). The the baseline reading is of standard to be used mg/L (or chosen units).
display will show mL, stable. The meter will (for example, 1.0 mL).
Sample, ?, and _ _ _ _. then prompt for the Press ENTER.
Use the number keys to standard volume. The Note: Obtain the standard
enter the sample volume, display will show mL, concentration and volume
then press ENTER. Standard, ?, and from Table 4 on page 45
_ _ _ _. after estimating the
sample concentration.
Note: Place the electrode
in the storage solution for
at least one minute to
prepare it for the next
standard.
43
Stabilizing... 20 mg/L
13. Add the volume of 14. Use the number 15. Sample+Standard 16. The meter will
a known standard (listed keys to enter the and Stabilizing... will be calculate and display the
in Table 4) to the beaker concentration of the displayed until the adjusted value for the
and proceed as quickly standard used (for reading is stable. original sample. Record
as possible through the example, 1000 mg/L). or store this value as
rest of the procedure. Press ENTER. usual.
Note: When recalling data
for standard additions,
STANDARD ADDITONS
will appear in the display
with the data.

Ammonia may be lost more quickly from samples at

temperatures above 50 °C, so it is important to collect samples at
less than 40 °C, or use a cooling coil between the bottle and
sampling point if necessary.


0.8 mL of concentrated sulfuric acid per liter. Use a sension pH
meter to be sure the pH of the preserved sample is between 1.5
and 2. Some wastewater samples may require more sulfuric acid
to achieve this pH. Store the sample at 4 °C. Samples preserved in
this manner may be stored up to 28 days.
44

Do not use mercuric chloride as a preservative as ammonia
Accuracy
interferences that may be present in the actual sample.
The spike should roughly double the measured concentration

without significantly diluting the sample. To run a standard
addition sample, use Table 4 to determine the concentration and
volume of standard to spike your sample. It is important that the
volume of sample transferred is accurate. Simply add the amount
and concentration specified in Table 4 to the sample while
performing the standard addition method on the sample. Do not
allow the sample to stand too long before spiking, as ammonia
will be lost to the atmosphere. Then proceed with the
calculations. Generally, results from 90-110% recovery are
considered acceptable.
Note: If distillation was not required, and you want to run a standard
addition, the following calculations are not correct. Use the
calculations following Table 1 on page 24.
Table 4 Spiking Volumes For Known Additions
Measured Sample Standard

Measured Sample
Concentration Concentration Standard Volume (mL)
Volume (mL)
(mg/L) (mg/L)
0.8–1.0 100 100 1.0
1–3 100 100 2.0
3–6 100 100 4.0
6–9 100 100 8.0
9–12 100 100 10.0
12–20 100 1000 2.0
20–40 100 1000 4.0
40–60 100 1000 6.0
60–75 100 1000 8.0
45

100 ( X s – Xu )
% Recovery = ---------------------------------
-
K
Where:
spike, in mg/L
Calculations
i X ×V u
1. X u = -----------------
-
Vu + V
Where:
Xi = measured value of unspiked sample in mg/L
C × V-
2. K = ----------------
Vu + V
Where:
Vu = volume of separate portion before spike in mL

100 ( X s – Xu )
% Recovery = ---------------------------------
-
K
Example:
A sample was analyzed and read 5.0 mg/L NH3-N. As directed in
Table 4, a 4.0-mL spike of 100-mg/L NH3-N standard was added
to another 100-mL sample, giving a final standard addition result
of 8.75 mg/L.

mg/L × 100 mL
1. X u = 5.0
-------------------------------------------------- = 4.81 mg/L
100 mL + 4 mL
mg/L × 4 mL
2. K = 100
--------------------------------------------- = 3.85 mg/L
100 mL + 4 mL
100 × ( Xs – X u ) 100 × ( 8.75 – 4.81 )

3. - = -------------------------------------------------- = 102.3 % Recovery
%R = ---------------------------------------
K 3.85
46
Method Performance
Precision
electrodes with a single sension4 meter, a single operator
Each electrode was exposed to seven test solutions and a default
stability of 0.5 mV/min. Between test solutions, the electrodes
were rinsed and placed in storage solution until a reading of
0.1 mV was obtained.
Interferences
Low molecular weight, volatile amines give a positive
interference. Mercury and silver interfere by complexing with
ammonia. Distillation prior to ammonia analysis removes all
inorganic interferences, such as metals which complex ammonia.
Comparison of Standard Method and Hach Method

Feature EPA Method 350.3 Hach Method 10001
Range ≥0.8 mg/L NH3-N ≥0.8 mg/L NH3-N
Preservation 2 mL H2SO4/L, 4 °C, 28 days 2 mL H2SO4/L, 4 °C, 28 days
Stock Solution(s) 1000 mg/L NH3-N 1000 mg/L NH3-N
Sample Size 100 mL 100 mL
NaOH Used 1 mL 10 N 1 mL 10 N
Electrode Hydrophobic gas permeable Hydrophobic gas permeable membrane
membrane
Electrode Internal Ammonium Chloride Ammonium Chloride
Solution
Electrometer pH meter with expanded mV pH meter with expanded mV scale of
scale of specific ion meter specific ion meter
Concentration Ratio Table 4500-NH3 IV Table 4500-NH3 IV encoded in software
Table
47
REQUIRED REAGENTS
Quantity Required
Ammonia Electrode Filling Solution...................................3 mL.......... 50 mL.......... 44472-26
Ammonia Electrode Storage Solution .................................5 mL........ 500 mL .......... 25412-49
Ammonia Nitrogen Standard, 1000 mg/L NH3-N.............. varies .............. 1 L.......... 23541-53
Sodium Hydroxide Solution, 10 N .....................................10 mL........500 mL .......... 25450-49
Water, deionized.................................................................100 mL............. 4 L.............. 272-56
REQUIRED APPARATUS
Ammonia Electrode ................................................................ 1 .................each .......... 50250-00
Bottle, wash .......................................................................................... 500 mL .............. 620-11
Cylinder, graduated, 100-mL .................................................. 1 .................each .............. 508-42
Stir Bar, 22.2 x 4.76 mm......................................................... 1 .................each .......... 45315-00
TenSette® Pipet, 1.0-10.0 mL ................................................. 1 .................each .......... 19700-10
Pipet tips for 19700-10 TenSette Pipet ................................................... 50/pkg .......... 21997-96
OPTIONAL REAGENTS
pH Paper, pH 9.0-12.0 ..................................................................... 5 rolls/pkg .............. 385-33
Sulfuric Acid, concentrated ...................................................................500 mL.............. 979-49
OPTIONAL APPARATUS
Pipet, Volumetric, Class A ....................................................................1.00 mL .......... 14515-35
Pipet, Volumetric, Class A ..................................................................10.00 mL .......... 14515-38
Pipet, Volumetric, Class A ..................................................................100.0 mL .......... 14515-42
TenSette® Pipet, 0.1-1.0 mL .......................................................................each .......... 19700-01
Pipet tips for 19700-01 TenSette Pipet .................................................. 50/pkg .......... 21856-96
sension™2 Portable pH/ISE Meter............................................................each .......... 51725-00
48
Method 8102
DIGESTION FOR LIQUIDS For Determining Ammonia Using TKN
1. Transfer a 2. Add 3 mL of 3. Turn the 4. Place the flask

premeasured amount of concentrated sulfuric temperature dial of the weight, followed by the
sample into the 100-mL acid (specific gravity Digesdahl to a setting of fractionating column
Digesdahl digestion 1.84) to the volumetric 440 °C (825 °F). When with funnel, on the flask.
flask. Select the flask. Add 2-4 silicon the proper temperature is Place the flask on the
appropriate amount from carbide (carborundum) reached, turn on the heater. Heat until
Table 1 below, based on boiling chips for liquid water to the aspirator. refluxing sulfuric acid
the expected TKN. The samples. Make sure there is and white acid vapors
amount transferred suction in the are visible.
Note: Before use, clean all
should not contain more glassware used in this fractionating column.
Note: Liquid samples
than 0.5 grams dry procedure with 1:1 nitric require total evaporation
Note: Wait for the proper
weight. The maximum acid and rinse thoroughly temperature to be reached of water before acid
volume of liquid sample with deionized water. before placing the sample vapors are visible. Allow
is 40 mL. In samples on the heater. 1 minute of heating per
Note: Before use, soak mL of wet sample. An
with more than 1% boiling chips for 24 hours Note: Always operate the additional 3-5 minutes of
solids present, use the in 1:1 nitric acid and rinse Digesdahl with a safety heating is then required.
formula below to thoroughly with deionized shield in place or inside of
determine the sample water. This is important a closed fume hood. Note: If sample foams,
volume: when working with low Safety glasses are lower the temperature to
40 - levels of ammonia
Sample Vol. = --------------------- mandatory. 355 °C. Heat until all the
% solids (<10 mg/L). Silicon water is evaporated.
So, if solids make up carbide chips are Return to original
10% of the total volume, recommended. digestion temperature and
the maximum volume of Note: Use only Hach heat until the boiling point
liquid sample would be Digesdahl digestion of sulfuric acid is reached.
4 mL. flasks. Do not use Note: If foaming/bumping
volumetric flasks with does not stop when the
concave bottoms. temperature is lowered or
less sample volume is
Table 1 Sample Volumes used, slowly add liquid
Expected TKN (mg/L) Sample Digestion Volume Multiplication Factor
samples that will not clog
the capillary funnel to the
1–10 40 mL 2.5 flask 10 mL at a time.
10–500 10 mL 10 Decrease the amount
100–10000 1 mL 100 added if foaming persists.
49
DIGESTION FOR LIQUIDS, continued
5. Heat 4 more 6. Do not proceed if 7. Boil off excess 8. Take the flask off the
minutes. Do not boil sulfuric acid is not hydrogen peroxide by heater and allow to cool
sample to dryness. If visible in the flask! Add heating for one more for 5 minutes. Remove
sulfuric acid is not 10 mL of 50% hydrogen minute after addition of the fractionating column
present in the flask after peroxide to the charred the hydrogen peroxide is from the digestion flask.
the 4 minute heating, do sample via the funnel on complete. Do not heat to Note: Use finger cots to
not proceed with step 6. the fractionating dryness. remove the digestion flask
If sample evaporates to column. and place on a cooling
dryness, discard it and Note: If the digest does
pad for several seconds.
use more sulfuric acid in Then remove the column.
not turn colorless, add
step 2 or choose a Do not add water to the
5-mL increments of
smaller sample amount flask until it has cooled.
hydrogen peroxide until
for digestion in step 1. the digest becomes clear
or the color of the digest
Note: Visually confirm the does not change upon
presence of sulfuric acid addition of hydrogen
in the flask before adding peroxide.
hydrogen peroxide.
9. When the flask is 10. Add 0.5 mL of 11. Neutralize the 12. Slightly acidify the
cool enough to handle, Thymol Blue Indicator sample by adding 10 N sample by adding 1.90 N
remove the weight and to the flask. The solution NaOH dropwise, until sulfuric acid dropwise,
add about 75 mL of should turn pink. the solution just turns until one drop turns the
ammonia-free deionized blue. This will take sample yellow. Stopper
water. Stopper and invert about 6 mL of 10 N the flask and invert it
several times to mix. NaOH. several times to make
sure the yellow color
persists.
50
13. Allow the flask to Continue with Method

come to room 10003, TKN Using the
temperature. Dilute to Ammonia ISE. The
the mark with ammonia- digestate may also be
free deionized water. used for samples that
The sample is ready for contain surfactants,
ammonia ISE making the use of the
measurement. Air Gap Accessory
unnecessary.
Note: A water bath or cool
tap water may be used to
cool the sample.
REQUIRED REAGENTS
Quantity Required
Description Per Digestion Unit Cat. No.
Hydrogen Peroxide, 50% ................................................... 10 mL ....... 490 mL ..........21196-49
Potassium Hydroxide Standard Solution, 1 N, SCDB* ......varies....... ...50 mL ..........23144-26
Potassium Hydroxide Standard Solution, 8 N.....................varies........ 500 mL ..............282-49
Sodium Hydroxide, 10 N .................................................... 6 mL ........ 500 mL ..........25450-49
Sulfuric Acid, ACS (conc., specific gravity 1.84).............. >3 mL ........... 2.5 L ..............979-09
Sulfuric Acid, 1.90 N, MDB ...............................................varies..... ...100 mL ..........21830-32
Water, deionized ..................................................................varies..........4 liters ..............272-56
REQUIRED APPARATUS
Boiling Chips, silicon carbide .............................................varies............500 g ..........20557-34
Dispenser, pour-out, 10 mL.................................................... 1................. each ..........22200-38
Flask, flat-bottom, volumetric, w stopper, 100 mL ................ 1................. each ..........23125-42
Pipet, serological, 10 mL........................................................ 1................. each ..............532-38
Pipet Filler, safety bulb........................................................... 1................. each ..........14651-00
Safety Glasses ........................................................................ 1................. each ..........18421-00
Safety Shield, for Digesdahl................................................... 1................. each ..........50040-00
* Contact Hach for larger sizes.
51
REQUIRED APPARATUS, continued

Description Unit Cat. No.
Digesdahl Apparatus, 115 Vac................................................ 1 .................each .......... 23130-20
Digesdahl Apparatus, 230 Vac................................................ 1 .................each .......... 23130-21
OPTIONAL REAGENTS
Hydrogen Peroxide, 30%, ACS ............................................................... 200 m.............. 144-45
Kjeldahl Reduction Reagent (for fluid fertilizers)...................................... 40 g .......... 23653-04
2,4-Dinitrophenol Indicator Solution, MDB..........................................100 mL............ 1348-32
Nitric Acid Solution, 1:1.......................................................................... 500 m............ 2540-49
Sodium Hydroxide, 5 N, Self Contained Dropper Bottle.............................. 50 mL............ 2450-26
Sodium Hydroxide, 1 N ........................................................................... 900 m............ 1045-53
TKN Indicator Solution, Self Contained Dropper Bottle ...........................50 mL .......... 22519-26
OPTIONAL APPARATUS
Balance, Precision, 115 V...........................................................................each .......... 26104-00
Balance, Precision, 220 V...........................................................................each .......... 26104-02
Beaker, 400 mL...........................................................................................each .............. 500-48
Beaker, Berzelius, 200 mL...................................................................... 12/pkg .......... 22761-75
Bottle, Wash, 1 L ........................................................................................each .............. 620-16
Bulb, dropper, 2 mL................................................................................ 12/pkg .......... 21189-00
Cylinder, graduated, 50 mL ........................................................................each .............. 508-41
Dispenser, Digital, 0.5-5.9 mL (for sulfuric acid, meat).............................each .......... 25631-37
Dispenser, Digital, 5-59 mL (for sulfuric acid, meat).................................each .......... 25631-41
Filter Discs, glass, 47 mm..................................................................... 100/pkg ............ 2530-00
Filter Holder, glass, 47 mm.........................................................................each ............ 2340-00
Flask, filter, 500 mL....................................................................................each .............. 546-49
Fume Scrubber Apparatus, 115 V...............................................................each .......... 23266-00
Fume Scrubber Apparatus, 220 V...............................................................each .......... 23266-02
Oven, laboratory, 120 V..............................................................................each .......... 14289-00
Paper, weighing, 76 x 76 mm ............................................................... 500/pkg .......... 14738-00
pH Paper, pH 0-14 ................................................................................ 100/pkg .......... 26013-00
Pipet, Pasteur, disposable, 229 mm....................................................... 200/pkg .......... 21234-01
Safety Glasses .............................................................................................each .......... 18421-00
Spatula, stainless, 10 cm .............................................................................each .............. 561-64
Spoon, measuring, 0.05 g............................................................................each .............. 492-00
Stir Bar, Teflon-coated, 25.4 x 7.9 mm.......................................................each .......... 20953-51
Stir Plate, magnetic, Thermolyne, 120V, 50/60 Hz ....................................each .......... 23444-00
Stir Plate, magnetic, Thermolyne, 240V, 50/60 Hz ....................................each .......... 23444-02
Stopper, hollow, size #5 ............................................................................ 6/pkg .......... 14480-05
Syringe, 5 cc, plastic ............................................................................. 100/pkg .......... 23433-33
Watch Glass, 65 mm ............................................................................... 12/pkg .............. 578-97
52
Method 10003
TOTAL KJELDAHL NITROGEN
Using the Ammonia ISE
1. Prepare the 2. Rinse the electrode 3. Connect the 4. Press ISE/MV until
electrode as described in and place it in the Ammonia ISE to the mg/L (or the user
Section 1.2 on page 10 Ammonia ISE storage meter. Verify that BNC selected concentration
Note: The module must
solution with the module is selected in Setup 1 of unit) appears.
be tightly screwed on. on to condition for at the Setup menu.
least 15 minutes. Note: The sension™4
Note: Use the Digestion
For Liquids procedure Note: Use Hach Ammonia meter has two BNC and
preceding this to digest Nitrogen Standards. They two five-pin connectors.
contain thymol blue to Choose one of the BNC
the sample before
indicate when the pH is connectors for the
analyzing for TKN.
high enough to begin ammonia electrode.
measurement.
53
TOTAL KJELDAHL NITROGEN, continued
Standard 1 ?
5. Press CAL. The 6. The display will 7. Fill a 50-mL beaker 8. Remove the
display will show CAL, show Standard 1 ? and to the 20-mL mark with electrode from the
?, mg/L, and the active the value of standard 1 a 1.0-mg/L NH3-N storage solution, rinse it
keys. The units will be from the previous standard. Add a stir bar with deionized water
flashing. Use the arrow calibration. If necessary, to the beaker. Place the and blot dry. Place the
keys to select the desired use the number keys to beaker on a magnetic electrode into the
units, then press ENTER. change the value to stirrer and stir at a 1.0-mg/L standard.
match the concentration moderate rate. Note: Before removing the
of the standard Note: Stirring at a electrode from the storage
(1.0 mg/L). Do not press constant rate speeds solution, the reading on
ENTER yet. response and improves the meter should be below
accuracy. For very 0.1 mg/L. This insures the
accurate work, use the electrode is properly
Hach Electromagnetic conditioned. After every
Stirrer to minimize heat hour of continuous use,
transfer to the sample. place the electrode in the
storage solution for 10
for accuracy and
54
Stabilizing... ----
9. Add one 1-g scoop 10. Add the contents 11. The display will 12. The display will
of sodium sulfate to the of one Ammonia ISA show Stabilizing... until show_ _ _ _ or the value
standard. Stir until all powder pillow. the reading is stable. of standard 2 from the
the solid is dissolved. Immediately press previous calibration.
ENTER. The meter will
Note: At a high pH,
ammonia solutions lose begin measuring the
ammonia to the standard. Proceed
atmosphere, lowering the immediately to the
concentration. It is next step.
important to take
is basic (turns blue).
Repeat steps
7-13
13. Place the electrode 14. Repeat steps 7-13 15. After the last 16. The display will
into the storage solution for the 10 and 100-mg/L standard is measured, show Store?. Press
for at least one minute. standards. press EXIT. ENTER to store the
Note: After the seventh
calibration or EXIT to
ISE standard, the meter leave the calibration
automatically displays the mode without storing the
STORE prompt. calibration values.
Note: Pressing REVIEW
will put the meter in
calibration review mode.
Be sure the slope is
–57 ±3 mV.
55
Stabilizing...
17. Fill a 50-mL 18. Remove the 19. Add the contents of 20. Stabilizing... will
beaker to the 20-mL electrode from the one powder pillow of be displayed until the
mark with digested storage solution, rinse it Ammonia ISA. reading is stable. Record
sample. Add a stir bar to with deionized water, Note: Do not add sodium
or store the
the beaker. Place the and blot dry. Place the sulfate to the digested measurement value.
beaker on a magnetic electrode into the sample. Repeat steps 17-20 for
stirrer and stir at a digested sample.
Note: At high pH, other samples.
moderate rate. Note: Before removing the ammonia solutions lose Note: It may take up to 10
electrode from the storage ammonia to the minutes for the probe to
solution, the reading on atmosphere, lowering the stabilize.
the meter should be below concentration. It is
0.1 mg/L. This insures the important to take
electrode is properly measurements as soon as
conditioned. After every possible after the solution
hour of continuous use, is basic (turns blue).
for accuracy and
Table 1 Sample Volumes

Recorded value
Sample Digestion
X Expected TKN (mg/L) Multiplication Factor
Volume
Multiplication
factor 1–10 40 mL 2.5
= mg/L TKN
10–500 10 mL 10
100–10000 1 mL 100
21. Calculate the TKN

value by multiplying the
recorded value by the
multiplication factor in
Table 1.
56

Collect samples in glass or polyethylene containers of convenient
size. Clean new bottles by washing with deionized or distilled
water. Fill the sample bottle completely and stopper immediately.
Analyze the sample as soon as possible. Ammonia may be lost
from samples at temperatures above 50 °C, so it is important to
collect samples at less than 40 °C, or use a cooling coil between
the bottle and sampling point if necessary. Use sodium thiosulfate
to destroy any residual chlorine immediately after collection so it
won’t react with ammonia in the sample. If prompt analysis is not
possible, preserve the sample with 0.8 mL of concentrated
sulfuric acid per liter. Use a pH meter to be sure the pH of the
preserved sample is between 1.5 and 2. Some wastewater samples
may require more sulfuric acid to achieve this pH. Store the
sample at 4 °C. Do not use mercuric chloride as a preservative as
ammonia complexes with mercuric ions. Before analysis,
neutralize the sample to pH 7 with 1 N sodium hydroxide.
Ammonia and Organic Nitrogen

Kjeldahl nitrogen is referred to as the sum of organic nitrogen and
ammonia. Organic nitrogen is defined as organically-bound
nitrogen in the trinegative oxidation state, whereas ammonia is
hydrogen-bound nitrogen in the trinegative oxidation state.
During digestion, all the organic nitrogen is converted to
ammonium and is then measured as ammonia. To determine the
free ammonia and organic nitrogen in a sample separately, run
analyses both with digested and undigested sample. The ammonia
value is obtained from the undigested sample. The organic
nitrogen is calculated by subtracting the ammonia value from the
TKN value (digested sample).
Accuracy and Precision

To verify sample measurement accuracy, run a standard addition
spike on the sample. This provides more complete information
about potential inaccuracies, because the measurement includes
any interferences that may be present in the actual sample. The
spike should roughly double the measured ammonia
concentration without significantly diluting the sample. To run a
standard addition sample, you may use Table 2 to prepare a
spiked sample for analysis, based on your measured sample
concentration. Primary standards for Kjeldahl Nitrogen are
57
available from Hach to be made into solutions which best suit

your particular application.
Note: The digest volume of To prepare the spiked sample, transfer 100 mL of sample to a
your spiked sample may clean 250-mL Erlenmeyer flask that has been rinsed with
not be the same as the ammonia-free deionized water. Add the appropriate volume and
digest volume of the
unspiked sample.
concentration of standard to the 100 mL of sample. Then proceed
through the digestion and analysis procedure.
Generally, results from 90-110% recovery are acceptable.

Table 2 Spiking Volumes For Known Additions
Digest
Measured Digest Spiked Sample
Measured Sample Standard
Sample Volume Standard Digest Volume
Concentration (mg/L) Concentration
(mL) Volume (mL) (mL)
(mg/L)
1–3 100 1000 0.2 40
3–5 100 1000 0.4 40
5–20 100 1000 1.0 10
20-100 100 1000 5.0 10
100–250 100 1000 10 10
250–425 100 1000 15 10
425–1000 100 10000 5 1
1000–3000 100 10000 10 1
3000–5000 100 10000 25 1

100 ( X s – Xu )
% Recovery = ---------------------------------
-
K
Where:
spike, in mg/L
K = known value of the spike in the sample, in mg/L.
58
Calculations:
Xi × Vu
1. X u = -----------------
-
Vu + V
Where:
Xi = measured value of unspiked sample in mL
C×V
2. K = -----------------
Vu + V
Where:
C = concentration of standard used in the spike, in mg/L
Vu = volume of separate portion before spike, in mL
V = volume of spike, in mL

100 ( X s – Xu )
% Recovery = ---------------------------------
-
K
Example:
A wastewater sample was analyzed and read 5.5 mg/L TKN. As
directed in Table 2, a 1.0-mL spike of 1000-mg/L NH3-N
standard was added to the 100-mL sample with a measured
concentration of 14.90 mg/L.

× 100
1. X u = 5.5
------------------------ = 5.44
100 + 1
2. Xu = 5.44 mL; Xs = 14.90 mg/L
1000 mg/L × 1 mL
3. K = ------------------------------------------------ = 9.90 mg/L
100 mL + 1 mL
100 × ( Xs – X u ) 100 × ( 14.9 – 5.44 )

4. %R = ---------------------------------------
- = -------------------------------------------------- = 95.5% Recovery
K 9.90
59
REQUIRED REAGENTS
Quantity Required
Ammonia Electrode Filling Solution.................................. drops.......... 50 mL.......... 44472-26
Ammonia Ionic Strength Adjustor (ISA)............................ varies ...... 100/pkg .......... 44471-69
Ammonia Electrode Storage Solution ................................25 mL........500 mL.......... 25412-49
1 mg/L NH3-N..............................................................20 mL....... 500 mL ...........1891-49
10 mg/L NH3-N............................................................20 mL....... 500 mL .............153-49
100 mg/L NH3-N..........................................................20 mL....... 500 mL ........ 24065-49
Hydrogen Peroxide Solution, 50% .....................................10 mL........500 mL.......... 21196-49
Indicator, Thymol Blue ...................................................... 3 drops ...... 100 mL .............. 257-32
Sodium Sulfate, ACS ............................................................ 3 g............. 454 g ............ 7099-01
Sulfuric Acid, 1.900 N........................................................ varies ....... 100 mL .......... 21830-32
Water, deionized.................................................................. varies .............. 4 L.............. 272-56
REQUIRED APPARATUS
Ammonia Electrode, combination, BNC................................ 1 .................each .......... 50250-00
Boiling Chips, silicone carbide............................................. 2-4 ............. 500g .......... 20557-34
Bottle, wash, 500 mL ..............................................................1 .................each .............. 620-11
Cylinder, graduated, 100 mL .................................................. 1 .................each .............. 508-42
Dropper, glass, 0.5-1.0 mL .....................................................1 ............... 5/pkg .......... 14197-05
Pipet, volumetric, Class A, 1.00 mL....................................... 1 .................each .......... 14515-35
Pipet, volumetric, Class A, 10.00 mL..................................... 1 .................each .......... 14515-38
Scoop, 1 g ............................................................................... 1 .................each .............. 510-00
Stir Bar, 22.2 x 4.76 cm .......................................................... 1 .................each .......... 45315-00


Digesdahl Digestion Apparatus, 115V ...................................1 .................each .......... 23130-20
Digesdahl Digestion Apparatus, 230V ...................................1 .................each .......... 23130-21
60
OPTIONAL REAGENTS
Description Unit Cat. No.
Primary Standards for Kjeldahl Nitrogen.............................................. set of 3 ..........22778-00
OPTIONAL APPARATUS DIGESDAHL

Safety Shield .............................................................................................. each ..........50040-00
Dispenser, variable volume, 1–5 mL.......................................................... each ..........25631-37
Pipet, TenSette, 0.1–1.0 mL ....................................................................... each ..........19700-01
Pipet, TenSette, 1.0–10.0 mL ..................................................................... each ..........19700-10
Pipet tips for 19700-01 TenSette® Pipet ................................................50/pkg ..........21856-96
Pipet tips for 19700-10 TenSette® Pipet ................................................50/pkg ..........21997-96
61
62
Method 10006
AMMONIA IN SOLUTIONS CONTAINING FATS,
FATTY ACIDS, OILS, AND SURFACTANTS
The Air Gap Accessory optimizes performance and extends the

usable lifetime of the membrane module. Samples containing
substances known to cause membrane failure (e.g., surfactants,
oils, fats) can be measured repeatedly with this accessory. Slopes,
absolute mV readings, and response times may change
significantly when the Air Gap Accessory is used. Therefore, use
the Air Gap Accessory for all calibrations and measurements.
Principle of Operation
The Ammonia Electrode uses a fine, porous membrane to
separate the sample solution from a thin layer of electrolyte that
coats the pH sensing bulb inside the electrode. Ammonia gas can
diffuse through, but other ions may not. When the Air Gap
Accessory is used, substances that can foul the membrane are
separated from the membrane by a small air space. Ammonia gas
diffuses through the air space and then through the membrane.
The air space has slightly different diffusion characteristics than
the membrane, which causes an increased response time.
63
AMMONIA IN SOLUTIONS CONTAINING FATS, FATTY ACIDS,
OILS, AND SURFACTANTS, continued
Assembling the Air Gap Accessory
1. Fill a membrane 2. Slide the Ammonia 3. With a clockwise

module and attach it to Electrode into the air twist, push the electrode
the Ammonia Electrode gap electrode holder, through the internal
as described in Section starting from the narrow O-ring until the
1.2 on page 10. end of the electrode electrode cap touches
Condition the electrode holder. the top of the electrode
in Ammonia Electrode holder. The electrode
Storage Solution for at normally stops about
least 15 minutes. 0.25 inches from the top
of the electrode holder
because of the O-ring.
Push the electrode
through the O-ring.
64
Calibration
1. Connect the 2. Turn the meter on. 3. Press SETUP. Press 4. Press ENTER and
Ammonia ISE to the Press ISE/mV until the the Up arrow until the use the numerical keys
sension™4 pH/ISE display shows mg/L (or display shows to edit the display until it
meter. Verify that BNC user selected Stabilizing... and a mV shows 0.1 mV/min.
is selected in Setup 1 of concentration units). value. Press ENTER, then press
the Setup menu. EXIT.
Note: Only the sension4
meter is recommended for
this method.
Note: The sension4 has

two BNC and two five-pin
connectors. Choose one
of the BNC connectors for
the ammonia electrode.
5. Fill the Air Gap 6. Add a stir bar to each 7. Add the contents of 8. Holding the cup
Accessory sample cup to cup. Place the cup the one Ammonia Ionic firmly with one hand,
the line with 1.0-mg/L 1.0-mg/L standard on a Strength Adjustor carefully insert the
NH3-N standard. stirrer. Stir at a moderate powder pillow to the cup electrode holder into the
rate. When the speed is on the stirrer. Do not stir. sample cup with a slight
Fill another sample cup
properly adjusted, turn twist to set the O-ring.
to the line with 10-mg/L
the motor off. Bubbling at the air vent
NH3-N standard.
may occur.
Note: Stir so there is
slight vortexing of the
sample in the cup.
65
Stabilizing...
9. Turn the stirrer on 10. After the two 11. The display will 12. The display will
and stir for 2 minutes. minute period, press show Standard 1, ?, and show Stabilizing... until
CAL. The display will the value of standard 1 the reading is stable. The
show CAL, ?, mg/L, from the previous display will then show
and the active keys. The calibration. Press _ _ _ _ or the value of
units will be flashing. ENTER to accept the standard 2 from the
Use the arrow keys to numerical value or use previous calibration.
select the desired units, the number keys to
Note: It may take up to
then press ENTER. change the value to five minutes for the
match the 1.0-mg/L electrode to stabilize.
concentration of the
standard, then press
ENTER.
13. Remove the 14. Rinse the electrode 15. Place the 10-mg/L 16. Holding the cup
electrode holder holder with deionized standard on the stirrer. firmly with one hand,
assembly by holding the water, including the Add the contents of one carefully insert the
sample with one hand on inside sample reservoir Ammonia Ionic Strength electrode holder into the
a horizontal surface and via the reservoir vent. Adjustor powder pillow sample cup with a slight
pulling out with a slight Gently blot the entire to the cup on the stirrer. twist to set the O-ring.
twist. Shake any excess holder. Turn the stirrer Do not stir. Bubbling at the air vent
sample off the holder off. may occur.
while keeping the holder
in a vertical position.
66
Repeat steps
Stabilizing... 13-19
17. Turn the stirrer on 18. Press ENTER to 19. The display will 20. Repeat steps 13-19
and stir for 2 minutes. accept the displayed show Stabilizing... until for each additional
value for standard 2 or the reading is stable. The standard.
use the numerical keys display will then show
to change the value to _ _ _ _ or the value of
10.0 mg/L, then press standard 3 from the
ENTER. previous calibration.
21. After the last 22. The display will 23. Press REVIEW. Use 24. Fill a sample cup to
standard is measured, show Store?. Press the Up arrow key to the line with sample.
press EXIT. ENTER to store the scroll to the last slope Add a stir bar.
calibration or EXIT to value. It should be
Note: After the seventh
standard, the meter leave the calibration -57 ±3 mV/decade.
automatically displays the mode without storing the Press EXIT to return to
STORE prompt. calibration values. measurement mode.
Note: If the slope is not
approximate -57 ±3
mV/decade, recalibration
may be necessary. If the
slope is still incorrect after
ammonia module.
67
Sample Measurement
Stabilizing...
25. Place the cup on 26. Holding the cup 27. Turn the stirrer on 28. The display will
the stirrer and stir at the firmly with one hand, and stir for 2 minutes. show Stabilizing... until
same speed as the carefully insert the the reading is stable.
standards. When the electrode holder into the Record or store the
speed is adjusted sample cup and twist value.
correctly, turn the slightly to set the O-ring.
stirrer off.
Repeat steps
24-31.
29. Remove the 30. Rinse the electrode 31. Repeat steps 24-31 32. After the last
electrode holder holder with deionized for each sample. sample, gently wash and
assembly by holding the water, including the blot the entire electrode.
sample in one hand on a inside sample reservoir Turn the stirrer off.
horizontal surface and via the reservoir vent. Be
pulling out with a slight careful not to rinse oils,
twist. Shake any excess sludge or surfactants
sample off the holder back into the air gap
while keeping the holder where the membrane is
in a vertical position. (it helps to retract the
electrode from the
electrode holder before
rinsing).
68

Collect samples in glass or polyethylene containers of convenient
size. Clean new bottles by washing with deionized or distilled
water. Fill the sample bottle completely and stopper immediately.
Analyze the sample as soon as possible. Ammonia may be lost
from samples at temperatures above 50 °C, so it is important to
collect samples at less than 40 °C, or use a cooling coil between
the bottle and sampling point if necessary.
Use sodium thiosulfate to destroy any residual chlorine

immediately after collection so it will not react with ammonia in
the sample.

0.8 mL of concentrated sulfuric acid per liter. Use a pH meter to
be sure the pH of the preserved sample is between 1.5 and 2.
Some wastewater samples may require more sulfuric acid to
achieve this pH. Store the sample at 4 °C.
Do not use mercuric chloride (HgCl2) as a preservative as

ammonia complexes with mercuric ions. Before analysis,
neutralize the sample to pH 7 with 1 N sodium hydroxide.
Accuracy Check
Checking Electrode Response
Note: Hach standard To verify electrode response, measure the electrode potential (in
concentrations are given mV) of two Ammonia nitrogen standard solutions, one decade
as elemental nitrogen (N), apart in concentration, that bracket the expected sample range.
not as NH3 or NH4+.
For example, use 10 and 100 mg/L ammonia nitrogen standards
to bracket an expected sample concentration of 30 mg/L. The two
standards should have potentials –57 ±3 mV apart at 25 °C.
Checking Calibration Accuracy

To verify calibration accuracy, measure the concentration of a
known standard within the calibration range.
69
REQUIRED REAGENTS
Quantity Required
Ammonia Electrode Filling Solution................................. 2 drops ........ 59 mL.......... 44472-26
Ammonia Electrode Storage Solution ................................20 mL....... 500 mL .......... 25412-49
Ammonia Ionic Strength Adjustor Pillows......................... varies ...... 100/pkg .......... 44471-69
1 mg/L NH3-N..............................................................20 mL....... 500 mL ............ 1891-49
10 mg/L NH3-N............................................................20 mL....... 500 mL .............. 153-49
100 mg/L NH3-N..........................................................20 mL....... 500 mL ......... 24065-49
Water, deionized.................................................................100 mL............. 4 L.............. 272-56
REQUIRED APPARATUS
Air Gap Accessory Kit............................................................ 1 .................each .......... 50253-00
sension™4 Laboratory pH/ISE Meter .................................... 1 .................each .......... 51775-00
OPTIONAL REAGENTS AND APPARATUS

Cylinder, graduated, 25 mL ........................................................................each .............. 508-40
Sulfuric Acid, concentrated .................................................................. 500 mL .............. 979-49
sension™2 Portable pH/ISE Meter............................................................each .......... 51725-00
TenSette® Pipet, 0.1-1.0 mL .......................................................................each .......... 19700-01
Pipet Tips, for TenSette® Pipet 19700-01.............................................. 50/pkg .......... 21856-96
70
SECTION 3 ANALYTICAL METHODS (mV meters)
71
72
DIRECT MEASUREMENT METHOD (with Graph Paper)
For meters that measure pH and millivolts, this method creates a
calibration curve by measuring the electrode potential of the
sample, then comparing this potential with potentials of
standards. The electrode potentials vs. concentrations are plotted
on a graph to make a calibration curve (see Figure 3). A best-fit
line is drawn through the points on the graph. Some ion or ISE
meters provide direct reading of the ammonia concentration. This
eliminates the need to plot a calibration curve unless the user
wants to verify the calibration curve.
Note: Most direct reading meters can only display results in the linear
part of the calibration curve. The advanced sension™2 and 4
pH/ISE meters can perform nonlinear calibrations, accurately
tracking electrode potentials in the nonlinear response region. This
eliminates manual plotting of calibration curves.
This direct method has some advantages:
1. It is fast— only one measurement per sample is necessary.

The known addition method requires two measurements per
sample and volumetric measurements of standards.
2. It covers a wide range of ammonia levels (see Figure 3),

including concentration in the low-level and non-linear
regions (see Figure 4).
Figure 3 Typical Calibration Curve
73
DIRECT MEASUREMENT METHOD (with Graph Paper), continued
Figure 4 Low Level Calibration Curve*
3.1 Preparing Standards for a Calibration Curve

The concentration and number of standards depends on the
expected sample concentration(s). If the samples have similar
ammonia concentrations and are in the linear response region
(0.5 mg/L NH3-N or 3.6 x 10-6 M), use a short method with two
standards that bracket the expected ammonia level. Standards
used for linear ISE calibration curves are usually one to two
powers of ten (or decades) apart in concentration. To cover a
wider range of concentrations, or measure below 0.5 mg/L, use
several standards (see Figure 3 and Figure 4). Standards may be
purchased or made by diluting a concentrated ammonia solution.
Hach sells 1000-, 100-, 10- and 1-mg/L NH3-N standards.
To prepare standards:
1. Using a Class A 100-mL volumetric pipet, measure 100 mL

of a concentrated standard (e.g., 100-mg/L NH3-N) into a
1000-mL volumetric flask.
* Relative mV values will vary from electrode to electrode.
74
2. Fill to the mark with ammonia-free deionized water. Mix
well. This is a ten-fold dilution of the original standard
(e.g., 10 mg/L).
3. Pour the solution into a 1-liter plastic container for storage.

Label the container and keep capped at all times.
4. Repeat steps 1-3 using the first dilution as the concentrated

standard. This is another 10-fold dilution (e.g., 1 mg/L).
Notes on Preparing Standards

• You may prepare a 100-mg/L NH3-N standard solution by
adding 0.3819 g of anhydrous ammonium chloride (oven
dried at 100 °C for 2 hours) to a 1000-mL volumetric flask.
Dilute to the mark with ammonia-free deionized water.
• Serial dilutions can be prepared from a 0.1-M standard,
producing 10-2 M, 10-3 M, and 10-4 M solutions.
• Ammonia concentrations can be expressed as:
mg/L ammonia as nitrogen (NH3-N)
mg/L ammonia (NH3)
mg/L ammonium (NH4+)
moles/L (M)
In this manual, concentrations are expressed in mg/L (ppm)
NH3-N and moles/L (M). See Ammonia Concentration Units
Conversion Table in the Appendix for conversions.
75
Procedure for Analysis Using a Manually Plotted Calibration Curve
1. Place the assembled 2. Select standards that 3. Pour the least 4. Add a clean
electrode in Ammonia cover the concentration concentrated standard magnetic stir bar. Place
Electrode Storage range of the samples. into a 50-mL plastic the beaker on a magnetic
Solution. Measure 25 mL of a beaker. stirrer and stir at a
standard solution in a moderate rate.
electrode from the storage graduated cylinder.
solution, the reading on
the meter should be below
for accuracy and
5. Place the electrode 6. Add the contents of 7. Prepare the next 8. Remove the
in the standard. one Ammonia ISA standard as in steps electrode from the
Powder Pillow, or add 2 and 3. previous standard. Place
0.10 g of ISA powder to it in Ammonia Electrode
the beaker. Record the Storage Solution for one
potential when it is minute.
stable.
76
Repeat for each

standard used
9. Rinse with distilled 10. Add the same 11. Repeat the above 12. On a sheet of
water and blot dry with a amount of ISA as was steps for all standards semilogarithmic graph
paper towel. Immerse added in step 6. Record used in making the paper (2-7 cycles), plot
the electrode in the new the potential when the calibration curve. the ammonia
standard. reading is stable. concentration values vs.
the potentials. Plot
concentrations on the
logarithmic (vertical)
axis. Each cycle is equal
to a 10-fold change in
concentration. Plot the
mV potential on the
linear (horizontal) axis.
See Figure 5 on page 80.
Note: Concentration units
may be ppm, mg/L,
moles/L or other
concentration units.
77
13. Draw a best-fit line 14. Approximate the

through the points. A slope:
straight line should a) Select two points on
connect the the straight portion of
concentrations above the curve that are one
0.5 mg/L NH3-N decade apart (e.g., 1 and
(3.6 x 10-6 M). 10 mg/L).
b) Subtract the potential
of the 1 mg/L standard
from the potential of the
10 mg/L standard.
c) The difference should
be -57 ±3 mV/decade (at
20-25 °C).
Measuring Samples
1. Place the electrode 2. Add a magnetic stir 3. Remove the 4. Add the contents of
into Ammonia Storage bar to the beaker. Place electrode from the one Ammonia ISA
Solution. Measure the beaker on a magnetic Ammonia Storage Powder Pillow or 0.10 g
25 mL of sample with a stirrer and stir at a Solution. Rinse with of ISA powder to the
graduated cylinder. Pour moderate rate. deionized water or a beaker with the sample.
it into a 50-mL plastic portion of the next
beaker. sample. Blot dry with a
paper towel (do not rub).
78
5. Immerse the 6. Using the calibration

electrode in the sample. curve (see Figure 5) and
Record the potential the example below
when the reading is determine the sample
stable. ammonia concentration.
Using the Calibration Curve
1. Refer to Figure 5. On the linear (horizontal) axis, locate the

potential value recorded in step 6 (I in the figure).
2. Draw a straight vertical line from the potential value up to the

calibration curve line (step b in the figure).
3. From that point on the curve, draw a straight horizontal line

across to the concentration (step c in the figure).
4. Read the point on the concentration line as the sample

concentration (step d in the figure).
79
Figure 5 Determining Sample Concentration using a Calibration Curve
Example
A water sample, measured using the above procedure, had a
potential of -108 mV. What is the ammonia concentration of
the sample?
Figure 5 is an example of a calibration curve. To find the

ammonia concentration of the sample, first locate the 108 mV
value on the vertical (linear) axis. Draw a vertical line from
108 mV to the calibration curve line. Then draw a line down to
the concentration scale on the horizontal (log) axis. The sample
concentration is about 10.5 mg/L NH3-N.
80
REQUIRED REAGENTS AND APPARATUS
Quantity Required
Ammonia Electrode, BNC ..................................................... 1................. each ..........50250-00
Ammonia Electrode Filling Solution, 60 mL......................varies............5/pkg ..........50287-05
Ammonia Electrode Storage Solution.................................varies....... 500 mL ..........25412-49
Ammonia Ionic Strength Adjustor Powder Pillows ............... 3............100/pkg ..........44471-69
10 mg/L NH3-N ......................................................... 20 mL ....... 500 mL ..............153-49
100 mg/L NH3-N ....................................................... 20 mL ....... 500 mL ..........24065-49
Beaker, 50 mL, polypropylene ............................................... 1................. each ............1080-41
Bottle, wash, 500 mL ............................................................. 1................. each ..............620-11
Graph Paper, semilogarithmic ................................................ 1............100/pkg ..........23062-01
sension™1 Portable pH Meter.............................................. 1................. each ..........51700-00
sension™3 Laboratory pH Meter ......................................... 1................. each ..........51750-00
Stir Bar, 22.2 x 4.76 mm ........................................................ 1................. each ..........45315-00
Water, deionized .................................................................varies............... 4 L ..............272-56
81
82
ANALYSIS WITH a pH/mV METER AND CALCULATOR
Also known as a linear calibration using two standards that
bracket the sample, this method is often used to calibrate for
direct measurements. The two-point calibration can be repeated
quickly and easily during each series of measurements. Figure 5
on page 80 is an example of a linear calibration curve.
Note: Use the two-point The two standards chosen should be close to the expected
calibration only in the linear concentration range of the samples. The standards often differ by
region. See Measuring only one decade.
Hints.
1. Place the electrode 2. Measure 25 mL of 3. Remove the 4. Place the electrode

in Ammonia Storage Standard 1. Pour it into a electrode from the into the standard
Solution. beaker. Add one powder Storage Solution, rinse solution. Record the
pillow or 0.5 mL of with deionized water potential when it is
electrode from the storage Ammonia ISA Solution. and blot dry. stable.
solution, the reading on Stir to dissolve the ISA.
the meter should be below
for accuracy and
83
ANALYSIS WITH a pH/mV METER AND CALCULATOR, continued
Repeat steps
1–4
5. Remove the 6. Repeat steps 1-4 7. Calculate the slope: 8. Measure 25 mL of

electrode from the with the second sample into a beaker.
standard and rinse with E 1 – E2
standard. Place electrode s = --------------------------------------------
-
deionized water. Blot in storage solution Log C 1 – Log C 2
dry with a paper towel when done.
(do not rub).
Where:
s = slope (mV/decade).
E1 and E2 = potentials of
standards 1 and 2.
C1 and C2 = the NH3

concentrations of
standards 1 and 2.
9. Add 0.5 mL of 10. Remove electrode 11. Place the electrode 12. Calculate the
Ammonia ISA Solution from Storage Solution. into the sample (stirring sample ammonia
or 0.5 mL of Ammonia Rinse and blot the increases accuracy and concentration using the
ISA Solution. Stir well. electrode. response time). Record equations following
the mV value when the this step.
display is stable.
84
Calculating the Ammonia in Samples
∆E = Ex – E 1
Where:
Ex = sample potential
E1 = standard potential (either standard)

∆E ⁄ S
C x = C 1 × 10
Where:
Cx = sample concentration
C1 = standard concentration (corresponding to E1)
S = the electrode slope
Example:
Standard 1 (C1) = 10.0 mg/L
E1 = -28.9 mV (potential of standard 1)
Slope (s) = -57.7 mV/decade
The sample (Ex) reads -10.4 mV
∆E = – 10.4 – ( – 28.9 ) = 18.5 mV

18.5 ⁄ – 57.7
C x = 10 mg/L × 10 = 4.78 mg/L
Measure the potentials of the standards periodically and compare

these values with the calibration values. If the potential of the
standard has changed, the offset potential has changed, and a new
calibration should be done.
Accuracy Check
To verify measurement accuracy, see Accuracy Check on page 23
in the Nitrogen-Ammonia in Water procedure (Method 10000).
85
Quantity Required
Ammonia Electrode Filling Solution, 60 mL ..................... drops............ 5/pkg .......... 50287-05
Ammonia Ionic Strength Adjustor Powder Pillows................ 3 .......... .100/pkg .......... 44471-69
10 mg/L NH3-N ..........................................................20 mL........500 mL.............. 153-49
100 mg/L NH3-N ........................................................20 mL........500 mL.......... 24065-49
sension™1 Portable pH Meter .............................................. 1 .................each .......... 51700-00
sension™3 Laboratory pH Meter.......................................... 1 .................each .......... 51750-00
Stir Bar, 22.2 x 4.76 mm......................................................... 1 .................each .......... 45315-00
Water, deionized ................................................................. varies ...............4 L .............. 272-56
86
Method 10007
MEASURING LOW LEVELS OF AMMONIA
For samples below 0.5 mg/L NH3-N
The electrode response is nonlinear below 0.5 mg/L NH3-N
(3.6 X 10-5 M). Low ammonia concentrations in the nonlinear
range can be determined by plotting a calibration curve, or by
using the sension™2 or sension™4 pH/ISE Meter. Use several
standards per decade to increase accuracy. Repeat or check the
calibration more often in this less stable, less reproducible region.
Use one of the calibration standards as a frequent check on the
stability of the calibration.
The method below measures all the standards in one beaker, with
spikes of ammonia standard added to incrementally raise the
ammonia level. Response time will be slightly longer in the
low-level range. If using a Hach sension4 meter, set the stability
criteria to 0.1 mV/min. Stirring at a constant rate is important and
using a chart recorder helps visualize the change in the potential.
87
MEASURING LOW LEVELS OF AMMONIA, continued
PROCEDURE
1. Fill a carefully 2. Add 8 powder 3. Rinse the electrode 4. Add 0.20 mL of

cleaned 600-mL beaker pillows (or 0.8 g) of thoroughly with 100-mg/L NH3-N
with 400 mL of Ammonia ISA. Place the deionized water and Standard Solution
deionized ammonia-free beaker on a magnetic place it into the beaker. (makes a 0.05 mg/L
water. Add a stir bar. stirrer and stir at a solution). Wait for the
moderate rate. potential to stabilize;
this may take up to five
Note: If the 400 mL of
sample requires more minutes. Record the
than 8 powder pillows of potential, or enter the
ISA to raise the pH above concentration into an
11 (solution turns blue) ISE meter calibration
run the calibration with the program.
amount of ISA necessary
to accomplish that. Before Note: The TenSette Pipet
calibrating, verify one ISA is useful for the repetitive
powder pillow added to additions used in this
50 mL of sample results in method.
a blue color.
88
5. Add 0.10 mL of 6. Add 0.10 mL of 7. Add 0.20 mL of 8. Add 0.60 mL of

100-mg/L NH3-N 100-mg/L NH3-N 100-mg/L NH3-N 100-mg/L NH3-N
Standard Solution Standard Solution Standard Solution Standard Solution
(makes a 0.075 mg/L (makes a 0.10 mg/L (makes a 0.15 mg/L (makes a 0.30 mg/L
solution). Record the solution). Record the solution). Record the solution). Record the
potential when it potential when it potential when it potential when it
stabilizes, or enter the stabilizes, or enter the stabilizes, or enter the stabilizes, or enter the
concentration into an concentration into an concentration into an concentration into an
ISE meter calibration ISE meter calibration ISE meter calibration ISE meter calibration
program. program. program. program.
9. Add 1.20 mL of 10. Enter the

100-mg/L NH3-N calibration into the
Standard Solution meter and accept. If you
(makes a 0.60 mg/L do not have a meter, plot
solution). Record the the concentration vs.
potential when it potential on semi-
stabilizes, or enter the logarithmic graph paper.
concentration into an The concentration goes
ISE meter calibration on the log axis, the
program. Store the potential goes on the
electrode in Ammonia linear axis (see Figure 5
Electrode Storage on page 80).
Solution until sample
measurement.
89
Sample Analysis
1. To determine the 2. Add at least 50 mL 3. Place stir bar in the 4. Place the electrode
sample concentration, of sample to a 100-mL sample beaker and stir at in the sample. Record
rinse the electrode and beaker. Add the a moderate rate on an the potential when it is
blot it dry. appropriate amount of electromagnetic stirrer. stable. Read the
ISA for the sample concentration from the
volume (one ISA ISE meter or the
Powder Pillow for every calibration curve.
50 mL or the amount
used in step 2 to adjust
for the sample pH).

Quantity Required
Ammonia Electrode Filling Solution.................................. varies ......... 59 mL.......... 44472-26
Ammonia Ionic Strength Adjustor Powder Pillows............ varies ....... 100/pkg .......... 44471-69
Ammonia (Nitrogen) Standard Solution,
100 mg/L NH3-N............................................................ 2.4 mL .......500 mL .......... 24065-49
Water, deionized.................................................................. varies ...............4 L .............. 272-56
Pipet Tips, for 19700 TenSette® Pipet ............................... varies ......... 50 pkg .......... 21856-96
Stir Bar, 22.2 x 4.76 mm......................................................... 1 .................each .......... 45315-00
TenSette® Pipet, 0.1-1.0 mL ................................................... 1 .................each .......... 19700-01
90
KNOWN ADDITION METHOD WITH A pH/mV METER
In the known or standard addition method, the analyst adds a

known amount of ammonia ion to the sample, then calculates the
original ammonia level from the change in potential. This
technique requires the electrode slope to be known and the
measurements to be in the linear region. The sension™4 has a
program that automatically calculates results for standard
additions. A calibration curve shows the linear region of the
probe and also the slope.
This method may be used when only a few samples need analysis.
It does not require a calibration curve and is a quick way to obtain
results on a few samples. This method produces the best results
when the ammonia level is doubled by the standard addition. This
requires knowing the approximate concentration of ammonia in
the sample, either from prior knowledge with the sample type or
estimating it from the potential using direct measurement (a
calibration curve is necessary).
1. Place the electrode 2. Using a volumetric 3. Add the contents of 4. Place the electrode
in Ammonia Electrode pipet, measure 50 mL of two Ammonia ISA into the sample.
Storage Solution. sample into a beaker. Powder Pillows (or 0.20
g of Ammonia ISA) to
electrode from the storage the beaker. Add a stir bar
solution, the reading on and place the beaker on
the meter should be below a magnetic stirrer. Stir
0.1 mg/L. This insures the moderately.
for accuracy and
91
KNOWN ADDITION METHOD, continued
5. Record the potential 6. Estimate the sample 7. Calculate the volume 8. Add the desired
when it is stable. ammonia concentration of ammonia standard to volume of standard into
using a calibration curve be added to roughly the sample.
or from previous double the ammonia
experience with the concentration:
same sample type. Vstd = Cs x Vs ÷ Χstd
Where:
Vs = sample volume
Cs = sample
concentration
See example following

these steps.
9. Record the potential 10. Calculate the

when it is stable, or enter sample concentration
the values prompted for using the second
by the ISE meter and equation and example
wait for the meter to following these steps.
measure the potential.
92
KNOWN ADDITON METHOD, continued
Example of Calculating the Ammonia Standard Volume

(from step 7)
How many mL of a 100-mg/L ammonia standard should be added
if the electrode potential of a 50-mL sample suggest the ammonia
level is about 1.0 mg/L?
1 mg/L × 50mL
V std = ---------------------------------------- = 0.50 mL
100 mg/L
Add 0.50 mL of standard to the sample. If this value is not easily
measured, round up to the next highest volume that is easily
measured.
Calculating Ammonia Concentration Samples (step 10)

Use these equations to calculate the sample ammonia
concentration:
∆E = E 2 – E 1
Where:
E1 = the sample potential
E2 = the potential after the spike
V std × C std
Sample ammonia = ------------------------------------------------------------------------------------------
∆E ⁄ s
( V sample + V std ) × 10 – V sample
Example
The sample potential is -53.9 mV. After adding 0.20 mL of a
1000-mg/L standard, the potential measures -72.2 mV.
E1 = -53.9 mV
E2 = -72.2 mV
∆E = -72.2 -(-53.9) = -18.3 mV
Vstd = 0.20 mL
Cstd = 100 mL
Vsample = 50 mL
s = -58.6 mV/decade (experimentally determined)
0.20 × 1000
C NH3-N = ------------------------------------------------------------------------------ = 3.8 mg/L
– 18.3 ⁄ – 58.6
( 50 + 0.2 ) × 10 – 50
93
KNOWN ADDITION METHOD, continued
REQUIRED REAGENTS
Quantity Required
Description Per Test Units Cat. No.
Ammonia Electrode Filling Solution, 5/pkg....................... varies ......... 59 mL.......... 50287-05
Ammonia Ionic Strength Adjustor Powder Pillows................ 2 .......... 100/pkg .......... 44471-69
Ammonia Standard Solution, 100 mg/L NH3-N ................ varies ........500 mL.......... 24065-49
Water, deionized.................................................................. varies .............. 4 L.............. 272-56
REQUIRED APPARATUS
Pipet, volumetric, 50 mL, Class A.......................................... 1 .................each .......... 14515-41
Pipet, TenSette®, 0.1 to 1.0 mL .............................................. 1 .................each .......... 19700-01
Pipet Tips, for 19700 TenSette® Pipet ............................... varies ......... 50 pkg .......... 21856-96
Stir Bar, 22.2 x 4.76 mm......................................................... 1 .................each .......... 45315-00
OPTIONAL APPARATUS
94
SECTION 4 ELECTRODE MAINTENANCE
4.1 Storing the Electrode

4.1.1 Short-term Storage
Between measurements or for low-level measurements, keep the
electrode tip immersed in Ammonia Electrode Storage Solution.
If the storage solution is not available, use pH 4 buffer. For low-
level measurements, keep the electrode in a pH 4 buffer between
measurements.
Do not store the electrode overnight in pH 4 buffer or

storage solution.
4.1.2 Long-term Storage

Overnight to One-Week Storage
Immerse the electrode tip in a 0.1 M or 1000 mg/L standard. Do
not add ISA.
Longer than One Week

Disassemble the electrode completely and rinse the inner body,
outer body, and bottom cap with deionized water. Dry and
reassemble the electrode without filling solution of a membrane.
When reassembling, follow the instructions in Section 1.2 on
page 10.
If the electrode is accidently left in the air and erratic results are
observed, the space between the inside of the membrane and the
sensing element may be dry. If this occurs, withdraw the glass
electrode from the membrane by gently pulling back on the
cables. New filling solution will flow into the space.
After storage, condition the electrode for at least one hour.
95
96
SECTION 5 ELECTRODE CHARACTERISTICS
5.1 Theory of Operation

The ammonia electrode uses a hydrophobic gas-permeable
membrane to separate the sample solution from the electrode
internal solution. Dissolved ammonia in the sample solution
diffuses through the membrane until the partial pressure of
ammonia is the same on both sides of the membrane. In any given
sample, the partial pressure of ammonia will be proportional to its
concentration. Ammonia diffusing through the membrane
dissolves in the internal filling solution and, to a small extent,
reacts reversibly with water in the filling solution:
NH3 + H2O ⇔ NH 4+ + OH-
The relationship between ammonia, ammonium ion, and

hydroxide is given by the following equation:
+ -
[ NH 4 ] [ OH ]
----------------------------------- = constant
[ NH 3 ]
The internal filling solution contains ammonium chloride at a

sufficiently high level so that the ammonium ion concentration
can be considered fixed. Thus:
-
[ OH ] = [ NH 3 ] × constant
The potential of the electrode sensing element with respect to the

internal reference element is described by the Nernst equation:
E = Eo– S log [OH-]
Where:
E = measured electrode potential
Eo = reference potential
OH- = hydroxide concentration in solution
S = electrode slope (–59.2 mV/decade)
Since the hydroxide concentration is proportional to the ammonia

concentration, electrode response to ammonia is also Nernstian.
E = Eo – S log [NH3]
The reference potential, Eo, is partly determined by the internal

reference element which responds to the fixed level of chloride in
the internal filling solution.
97
5.2 Electrode Response

The electrode exhibits good time response (95% response in one
minute or less) for ammonia concentrations above 4 x 10-5 M
(0.68 mg/L NH3 or 0.56 mg/L N). Below this value response
times are longer, and ammonia absorption from the air may
become a source of error. Above 1 M, ammonia is rapidly lost to
the air. Samples above 1 M ammonia concentration can be diluted
before measurement. Figure 6 shows response time of the
ammonia electrode to step changes in ammonia concentration.
For solutions low in ammonia but high in total ionic strength,

prepare a calibration solution with a composition similar to the
sample. Accurate measurement requires these conditions:
• Allow adequate time for electrode stabilization. Longer

response time will be needed at low levels.
• Stir standards and samples at a uniform rate.
When plotted on semilogarithmic paper, electrode potential

response as a function of ammonia concentration is a straight line
with a slope of about -58 mV per decade.
Figure 6 Response to Step Changes
98
5.3 Reproducibility
Reproducibility is limited by factors such as temperature
fluctuations, drift, and noise. Within the operating range of the
electrode, reproducibility is independent of concentration. With
calibration every hour, measurements to ±2% can be obtained.
5.4 Temperature Effects

A change in temperature will cause electrode response to shift
and change slope. Table 3 lists the variation of theoretical
response with temperature. At 10-3 M, a 1 °C temperature change
causes a 2% error. Samples and standards should be at the same
temperature (for convenience, room temperature). As the
temperature increases, so does the ammonia loss.
Table 3 Theoretical Slope vs. Temperature
Temperature (°C) Slope (mV)
0 -54.20
5 -55.20
10 -56.18
15 -57.17
20 -58.16
25 -59.16
30 -60.15
35 -61.14
40 -62.13
5.5 Effect of Ionic Strength

Water vapor is a potential electrode interference. Water can move
across the membrane as water vapor, changing the concentration
of the internal filling solution under the membrane. Such changes
will be seen as electrode drift. Water vapor transport across the
membrane is not a problem if:
1. The total level of dissolved species in solution (osmotic

strength) is below 1 M.
2. Electrode and sample temperatures are the same.
99
Adding ammonia ISA to samples of low osmotic strength

automatically adjusts them to the correct level. Samples with
osmotic strengths above 1 M should be diluted before measuring
ammonia levels below 10-5. Samples with high osmotic strengths
(above 1 M) and low ammonium levels (below 10-5 M) can be
measured without dilution if the osmotic strength of the internal
filling solution is adjusted. To adjust the internal filling solution,
add 4.25 g solid NaNO3 to each 100 mL internal filling solution.
5.6 Interferences
Volatile amines interfere with electrode measurement. Most gases
do not interfere as they are converted to ionic form in basic
solutions. Ionic species cannot cross the gas-permeable
membrane and are not direct electrode interferences. However,
the level of ions in solution can change the solubility of ammonia.
Standards and samples should have about the same level of ions
and dissolved species.
Ammonia forms metal complexes with a number of metal ions:

mercury, silver, copper, gold, nickel, cobalt, cadmium, and zinc.
At pH 11, most of these metals form hydroxide complexes or
precipitate. When hydroxide is present at the 0.1 M level and the
ammonia concentration is below 10-3 M, only mercury will
appreciably complex ammonia. The total ammonia level of the
sample will be measured if the mercury in the sample is
preferentially bound to some other species. Iodide is
recommended for this purpose, since it forms a soluble mercury
complex at all pH levels. Use of Ammonia ISA inhibits the
formation of some common metal complexes in the sample
because it contains a high concentration of hydroxide ion.
5.7 Ammonium Ion

When ammonia is dissolved in water it reacts with hydrogen ion
to form ammonium ion:
NH3 + H30+ ⇔ NH4+ + H20
The relative amount of ammonia and ammonium ion is

determined by the solution pH. In acid solutions, where hydrogen
ion is readily available, virtually all the ammonia is converted to
ammonium ion. At a pH of about 9.3, half of the ammonia will be
in the form of ammonium.
100
Theoretically, it is possible to calculate the ratio of ammonia to

ammonium ion, if the pH is known. The equilibrium constant of
the reaction is:
+ +
[ NH 4 ] [ NH 4 ] 10 – 9.3
- = ------------------------------------- = K
-----------------------------------
+
[ H 3 O ] [ NH 3 ] 10 – pH [ NH 3 ]
at 25°, µ = 0.1 and pK = 9.3. The ratio of ammonium to ammonia

is given by:
+
[ NH 4 ] 9.3 – pH
------------------- = ( K10 – pH ) = 10
[ NH 3 ]
5.8 Partial Pressure of Ammonia

As discussed in Theory of Operation, the ammonia electrode
responds to the partial pressure of dissolved ammonia gas. The
partial pressure of dissolved ammonia gas is related to the
ammonia concentration by Henry's Law:
NH 3 aqueous
Kh = ---------------------------------- = 56 moles/liter – atm (25 °C)
pNH3
The Henry's Law constant, Kh, varies both with temperature and
the level of dissolved species. For example, the constant is about
20% lower in 1 M NaCl than in distilled water.
To keep the Henry's Law constant close to the same value,

standards and samples should contain the same level of dissolved
species and be about the same temperature.
5.9 Electrode Life

A membrane will last from one week to several months
depending on usage (membrane failure is characterized by a shift
in electrode potential, drift, and poor response).
Membrane failure may be apparent on visual inspection as dark

spots or discoloration of the membrane.
101
102
SECTION 6 TROUBLESHOOTING
This section contains a series of decision trees based on the
symptoms that result from a problem or a combination of
problems. The symptoms are listed below along with the page
number of the decision tree that will help solve the problem(s)
that may cause the symptom.
Before using a decision tree, check the pH bulb per Section 6.1
Symptom Page
Inaccurate readings 104
Imprecise readings 104
Low slope or no slope 105
Drift in the meter reading 107
Slow response time 107
Error messages or no key response See meter manual
6.1 Checking pH Bulb Function

1. Unscrew the Ammonia Membrane Module and remove it.
2. Rinse the electrode with deionized water.
3. Use pH 4 and 7 buffers (add 0.5 gram sodium chloride per

50 mL of buffer). Carefully immerse the pH bulb in the pH 4
buffer. Record the mV reading.
4. Immerse the pH bulb in the pH 7 buffer. Record the mV

reading.
5. Subtract the pH 7 mV reading from the pH 4 mV reading.

Divide the difference by 3. The answer should be -57 ±3 mV.
103
6.2 Decision Trees

Symptom: Accuracy or precision is in question.
104
Symptom: Low Slope
105
106
Symptom: The meter reading is slow, drifting, jumpy or dramatically offset.
107
108
ELECTRODE SERVICE REQUEST QUESTIONNAIRE
If the electrode still malfunctions after following the
troubleshooting guide, our service representatives want to help
solve any problems as quickly as possible. To help them with this
process, please have the following information when calling:
1. The electrode catalog number.
2. Model of the meter the electrode is being used with.
3. Complete lot code of the electrode.
4. Date the electrode was purchased.
5. How long the electrode has been in use.
6. How often the electrode is being used.
7. Types of samples being tested.
8. Has ISA been used in all samples and standards?
9. How the electrode is stored between samples.
10. Slope of the electrode after a typical calibration.
11. If the electrode is new, how was it conditioned?
12. Any maintenance that has been done on the electrode.
13. Any long-term storage periods and how it was stored.
14. Does a visual inspection show any cracks, discoloration,

broken wires, crystals, etc.
15. Description of the problem.
109
110
GLOSSARY
Acid —A chemical compound that contributes hydrogen ions
(H+) to an aqueous solution or causes the pH to be less than 7.0.
Acidic—A solution or system with a pH less than 7.0.
Activity—The measure of work performed by an ion as it moves

through a system. The activity is dependent upon the
concentration of all ions in the system and the charge associated
with the ion.
Alkali—A solution or system with a pH greater than 7.0.
Alkalinity—Capacity of water to accept hydrogen (H+) ions.

Characteristic of the presence of carbonate (CO32-), bicarbonate
(HCO3-), and hydroxyl (OH-) ions.
Anion—A negatively charged ion (i.e., NO3-, Cl-).
Base—A compound that contributes hydroxide ions (OH -) to an

aqueous solution or causes the pH to be greater than 7.0.
Buffer—1. A compound, mixture of compounds, or solution

which when added to a system changes the pH to a specified,
known value.
2. The ability of a solution or system to resist change in pH when

either an acid or a base is added.
Buffering Capacity—A measurement of the amount of acid or

base which can be added to a solution before the pH changes.
Cation—A positively charged ion (i.e., NH4+, Ca2+).
Chelating Agents—Organic compounds that can withdraw ions

from solution, forming complexes in which the species removed
is not available for measurement. The complex formed may or
may not be insoluble.
Decade—Any two standards with a concentration ratio of 10; i.e.,

Concentration of higher standard
--------------------------------------------------------------------------------------- = 10
Concentraion of lower standard
Dilution Factor—A numerical value by which results must be
multiplied in order to obtain the actual value of the sample. For
example, if one mL of sample is diluted to 10 mL then the result
111
GLOSSARY, continued
obtained must be multiplied by 10 to obtain the value for the

sample before dilution.
Electrolyte—A solution comprised of dissolved ions used to

facilitate electrical conductance and ionic transport. In
electrochemistry, the composition is usually potassium chloride
(KCl), sodium chloride (NaCl), ammonium chloride (NH4Cl), or
ammonium sulfate ((NH4)2SO4).
Inert—Does not react with other substances.
Ion—An atom, group of atoms or molecule that is electrically

charged as the result of gaining or losing electrons. An ion
resulting from the gain of electrons becomes negative (anion); an
ion resulting from the loss of electrons becomes positive (cation).
Ionic Strength Adjustor—A powder or solution that changes the

ionic strength of a sample and adjusts the pH. Typically used to
mask or moderate common interferences while adjusting the pH
to the optimum operating range.
ISA—See Ionic Strength Adjustor.
Linear Response Region—The operating range of the electrode

where the calibration curve is a straight line.
Nonlinear Response Region—The operating range of the

electrode where the calibration is not a straight line. It is usually
at the lowest concentration range of the electrode
pH—A relative numerical measurement of the acidic, neutral, or

alkali nature of a solution or system. Mathematically defined as
the negative log of the hydrogen ion concentration.
Potential—The capacity of a system to perform work. When two

ions of opposite charge are separated, a potential develops from
the tendency of the ions to come together. Each ion would need to
exert work to come together. The amount of work that each ion
would need to exert to come together is the potential.
Salt—An ionic compound.
TISAB—Total Ionic Strength Adjustor Buffer; See Ionic

Strength Adjustor.
112
GENERAL INFORMATION
At Hach Company, customer service is an

important part of every product we make.
With that in mind, we have compiled the

following information for your convenience.
113
114
APPENDIX CONVERSION TABLES
Table 4 Ammonia Concentration Conversions
Moles/L mg/L NH3 mg/L NH3-N mg/L NH4+

(M) (ppm) (ppm) (ppm)
1 x 10-1 1700 1400 1800
-2
1 x 10 170 140 180
1 x 10-3 17 14 18
-4
1 x 10 1.7 1.4 1.8
-5
1 x 10 0.17 0.14 0.18
-6
1 x 10 0.017 0.014 0.018
Table 5 Ammonia Unit Conversions
To convert from... To... Multiply by...

moles/L (M) mg/L NH3 17,000
mg/L NH3 mg/L NH3--N 0.822
-
mg/L NH3 -N mg/L NH4+ 1.29
mg/L NH3 moles/L (M) 5.87 x 10-5
mg/L NH3--N mg/L NH3 1.22
+
mg/L NH4 mg/L NH3--N 0.776
115
116
HOW TO ORDER
117
REPAIR SERVICE
118
WARRANTY
119

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51940-88

Ammonia Gas Sensing

SECTION 1 INTRODUCTION ........................................................................................ 9

SECTION 2 APPLICATIONS (sension™2 & 4 meters) ........................................... 17

SECTION 3 ANALYTICAL METHODS (mV meters) ............................................ 71

SECTION 4 ELECTRODE MAINTENANCE ........................................................... 95

SECTION 5 ELECTRODE CHARACTERISTICS .................................................. 97

SECTION 6 TROUBLESHOOTING.......................................................................... 103

ELECTRODE SERVICE REQUEST QUESTIONNAIRE .................................................. 109

GENERAL INFORMATION....................................................................................... 113

Ammonia Membrane Modules

Internal Filling Solution

1.1 Electrode Description

Figure 1 Ammonia Gas Sensing Electrode

The gas-permeable membrane separates the sample from a thin

in the thin layer of electrolyte. The potential across the pH glass

The ammonia electrode will measure ammonia gas or ammonium

1.2 Preparing the Electrode For Use

1. Soak the inner body in Ammonia Electrode Filling Solution

3. Screw an ammonia module into the end of the electrode outer

4. Fill the outer body with about 2.5 mL of Ammonia

6. Shake the fully assembled electrode as if it were a

Figure 2 Assembling the Electrode

1.2.1 Ammonia Modules and Membranes

Avoid excessive handling of the modules during assembly as this

Membrane failure will cause a shift in electrode potential, drift

1. The electrode response becomes very slow.

2. The results are not reproducible.

3. The slope becomes too low or shifts.

4. Visual inspection detects dark spots or discoloration of

Ammonia membranes without the end cap are also available. To

1. Remove the used membrane (or membrane module) from

2. Locate an end cap (without membrane) and put it where it

3. Carefully separate a membrane from the others. Handle only

5. Lay the membrane on top of the sensing end of the electrode.

1.2.2 Replacing the Internal Filling Solution

1. Unscrew the membrane module. Pour out the filling solution.

2. Rinse the pH bulb and reference wire with deionized water

3. Fill the module with new solution to the bottom of the

4. Screw the membrane module onto the electrode body. Excess

1.2.3 Conditioning the Electrode

1.2.3.2 Between Samples

1.2.3.3 Overnight and Up to One Week

1.2.3.4 Longer Than One Week

1.3 Checking The Ammonia Electrode Slope

2. If using a Hach sension™2 meter, go to step 3. If using a

4. Using a 25-mL graduated cylinder, measure 25 mL of each

5. Add the contents of one Ammonia Ionic Strength Adjustor

6. Place the beaker on a magnetic stirrer and stir at a moderate

7. Place the electrode into the beaker being stirred. When a

8. Remove the electrode and rinse with deionized water. Blot

9. Prepare the higher standard as in steps 4 and 5. Immerse the

10. Record the mV potential when it is stable.

1.4 Measuring Hints

• Two alternatives exist for handling solutions that contain oils,

NH4+ or NH3 in the sample and is not appropriate for

• To improve response time and the reproducibility of the

• Check the electrode for accuracy after every hour of use in

• Make sure all samples and standards are at the same

• For best accuracy, especially at low levels where long sample

• Excessive mixing or stirring causes rapid diffusion of

• Add the correct amount of Ionic Strength Adjustor (ISA) to

• Measure samples and standards within 15 minutes after