1.

5 Ammonia Analyzers
d. C. gAllego (2017)

Methods of detection Industrial Automatic Methods

Liquids:
A. Colorimetric
B. ISE (Ion Selective)
C. UV Spectrophotometry
Gases:
D. NIR (Infrared Spectrophotometry)
E. Mass Spectrophotometry
F. TDL (Tunable Diode Laser)

Measurement cycle Liquids:

I. Colorimetric and UV methods: between 3 and 15 min, when calibration cycle required between 15 and 40 min
II. ISE method: continuous measurement
Gases:
III. IR and Mass spectrophotometer: long cycles due to sample conditioning before analysis cycle (10–15 min)
IV. TDL open path: continuous measurement
V. TDL extractive: less than 15 min

Accuracy Liquids:
a. Colorimetric: ±0.005 ppm
b. ISE: ±0.02 to 0.5 ppm to 500ppm if the range is higher 7.5% of the full scale
c. UV: 10% of full scale

Ranges Liquids:
a. Colorimetric: 0–3 ppm
b. ISE: 0.5–1000 ppm of NH3
c. UV: FFT 0–1000 mg/l and UV chloramine method 0–500 mg/l

Price Liquid:
a. Colorimetric: Approximate price between $10,000 and $15,000
b. ISE: Approximate price between $10,000 and $15,000
c. UV: Approximate price between $35,000 and $40,000
Gases:
d. TDL: Approximate price between $50,000 (in situ) and $120,000 (extractive)

Partial list of suppliers ISE:

ABB (http://www.abb.com/product/us/9AAC100044.aspx)
Emerson (http://www2.emersonprocess.com/en-US/brands/rosemountanalytical/Liquid/Systems/WQP/Pages/index.aspx)
Endress + Hauser (http://www.endress.com/eh/home.nsf/#page/~product-news-nitrification-denitrification-control-isemax)
Yokogawa (www.yokogawa.com)
Colorimetric:
ABB (http://www.abb.com/product/us/9AAC100044.aspx)
ASA Analytics (http://www.asaanalytics.com/chemscan2150S.php)
UV:
Chemitec (http://www.chemitec.it/images/catalogo/Chemitec_Catalogo_Inglese_Analysers.pdf)
Dtli (http://www.datalink-instruments.com/index.php?nav=3)

109
110 Analytical Measurement
IntroduCtIon
The measurement of ammonia and ammonium ion concen-
tration or traces (in gases or liquids) is very important in
many industrial and environmental processes.
This chapter includes industrial measurement techniques
for concentration determination. These techniques may be
separated into measurements in liquids and measurements in
gases.
Measurement in liquids is usually performed with colo-
rimetric, ion selective, and/or UV spectrophotometric meth-
ods. However, measurement in gases is typically carried out
using NIR spectrophotometry, mass spectrophotometers, or
tunable diode lasers (TDL).
AMMonIA MeAsureMent In lIQuIds
Ammonia measurement in liquids other than water can be
performed by using chromatographs although these mea-
surements are rarely required. The most common measure-
ment is ammonia in water.
Ammonia is very soluble in water and other liquids. In
water, ammonia exists simultaneously in two different condi-
tions: as free unionized gaseous ammonia (NH3) and as the
ionized ammonium ion (NH4+). The ratio of NH3 to NH4+
that exists in water depends mostly on the pH and in a lesser
degree on the temperature:
• At 25°C a sample with pH 7.25 is mostly NH4+.
• At 25°C a sample with pH 9.25 contains similar amounts
of NH3 and NH4+.
• At 25°C a sample with pH 11.25 is mostly NH3.
The most common application is the measurement in water
treatment plants in order to determine water quality. The
ammonia concentration, even in low concentrations, deter-
mines the presence of fecal bacteria or pathogens and, there-
fore, a poor water treatment or water pollution.
To determine the ammonia concentration in water the
following methods can be used:
• Colorimetric: The ammonia concentration is deter-
mined by using a phenate that produces the reaction
of a phenol and hypochlorite with ammonia to create
a blue-colored compound. The color intensity is pro-
portional to the ammonia concentration.
• ISE Ammonia Selective Electrode: This method is
probably the easiest one to perform. After the pH has
been adjusted to 11, the ammonia solution diffuses
through a special membrane at the tip of the electrode.
The change in electrical potential at the electrode is
proportional to the ammonia concentration.
UV Spectrophotometry analysis. See Chapter 1.69.
These analysis methods can be either continuous or
discontinuous with analysis cycle time of up to 50 min.
ColorIMetrIC Method
This method is based on the Berthelot reaction or indophenol
method (see Chapter 1.15). The ammonia and all the ammo-
nia compounds react with phenol giving place to indophe-
nol. This reaction is described with Equations 1.5(1) through
1.5(3). Ammonia (NH3) reacts with hypochlorite (NaOCl)
to form a monochloramine, see Equation 1.5(1), which in
turn reacts with two phenates to form an indophenol, see
Equations 1.5(2) and 1.5(3). The stoichiometry of the overall
reaction tells us that 1 mol of NH3 reacts with 2 mol of phe-
nate and 3 mol of NaOCl to form 1 mol of indophenol. The
concentration of NH3 is determined by measuring the absor-
bance spectrum of indophenol at λ = 630 nm. The obtained
color intensity determines the ammonia concentration. In
these reactions, NH2Cl, NaOH, and phenol are important
reagents for the indophenol formation.
NH3 + NaOCl NH2Cl + NaOH 1.5(1)
NH2Cl + ONa + 2NaOCl
Cl–N O + 2NaCl + H2O + NaOH 1.5(2)
Cl–N O + ONa
HO N O + NaCl 1.5(3)
A previous step of membrane filtration is required in
order to avoid possible interferences caused by turbidity in
the sample.
For the analysis, three reagents are necessary, requiring
that online analyzers must have a periodic maintenance in
order to refill the tanks with the reagents.
These online analyzers have an analysis cycle time
between 3 and 15 min.
The calibration and cleaning cycle varies between 15 and
45 min.
The typical measurement range for these analyzers is
0–3 ppm.
 1.5 Ammonia Analyzers 111

In Figure 1.5a, a typical configuration for an ammonia Ion-seleCtIVe Method (Ise)

colorimeter in water is shown. Figure 1.5b shows the mea-
surement cell. This analyzer uses the ISE methods (see Chapter 1.33)
for laboratory use ASTM D1426. In order to measure dis-
solved ammonia, this method requires an alkali (sodium
hydroxide) reagent to treat the sample and measure all
ammonia compounds (NH 3 and NH4 +). The sodium
hydroxide releases the available ammonia in a free form
by adjusting the pH of the sample solution to a value
greater than 11.
A permeable membrane is in contact with the water
and this membrane allows the free ammonia to pass into
contact with the NH4Cl. This last compound is the liquid
Sample fill inside the membrane that reacts with the free ammo-
outlet(s) to
waste
nia and changes the pH of the ammonium chloride NH4Cl
Sample in
solution.
The ISE probe measures the change of pH produced in
Air in
Waste
the ammonium chloride solution. These pH changes are
from proportional to the concentration of free ammonia in the
sample
outlet(s) solution.
Figure 1.5c shows a complete system with a peristaltic
pump and a reagent dosing system.

2 1
3
Reagents Cable entries
Standard
Waste Deionised water Display (both sides
of case)
Fig. 1.5a Liquid-handling
section access door
Multistream ammonia in water colorimeter analyzer. (Courtesy of Keypad
ABB Analytics.)

Peristaltic pump
Mixer assembly
(fluoride analyzer
only)
Temperature-controlled
probe housing block
containing ammonia or
fluoride probe
Precisely
controlled Solenoid valves
stepper motor

Optical glass Fig. 1.5c

measurement ISE ammonia water analyzer. (Courtesy of ABB Analytics.)
Temperature- cell
controlled
inner body
assembly
Piston
assembly

LED
light source
Detector

Fig. 1.5b
Measurement cell of colorimeter. (Courtesy of ABB Analytics.)
112 Analytical Measurement
Reagent
pump
Standard Standard Sample from Reagent
solution (low) solution (high) side-sample pot
Fig. 1.5d
Flow schematic of ISE ammonia analyzer. (Courtesy of ABB Analytics.)
The flow schematic of this system is shown in Figure 1.5d.
This type of analyzer requires less maintenance than the
analyzers using a colorimetric method as the only reagent
used is the NaOH.
This type of analyzer is intended for continuous measure-
ment but it is very important that the sample does not contain
elements that can saturate the permeable membrane.
uV sPeCtroPhotoMetry Method
The general operation of this method is described in Chapter
1.69 of this book.
The ammonia determination in water using UV spectro-
photometry techniques can be accomplished using two dif-
ferent methods:
• Measuring the ammonia in gaseous phase
• Measuring ammonia converted into monochloramine
Measuring the ammonia in gaseous phase: The measurement
principle is based on the UV light absorption spectrum of ammo-
nia gas NH3 in equilibrium with dissolved ammonia gas in the
water sample. A small quantity of sodium hydroxide (NaOH)
is added to the sample to increase the pH for transforming
NH4+ into NH3. A fast Fourier transform (FFT) is applied to the
spectrum in order to extract the typical absorption signal of the
ammonia gas. This method is very selective and it is suitable for
river or waste water applications where other compounds might
be present. Furthermore, turbidity or water coloring has no influ-
ence since the measurement is performed in gaseous phase.
Measuring ammonia converted into monochloramine: This
type of analyzer is based on the UV light absorbance of mono-
chloramine for ammonia concentration determination. Its
absorbance is located in wavelengths between 200 and 450 nm.
The analyzer comprises, like all UV spectrophotometers, a
UV radiation source, a sample cell, a dispersion device, and a
photodiode array (detector). The difference with a general UV
spectrophotometer can be found in the treatment of the sample
since for the measurement of the ammonia it is required that
it has previously been converted into chloramines. This can
be achieved first by adding NaOH to adjust the pH to a value
Conditioned
sample Electrode
support block
Waste (red)
greater than 12 and then by adding hypochlorite to convert all
the remaining ammonia into monochloramine. The mono-
chloramine is the substance that will absorb the UV radiation.
Some UV ammonia analyzers use multiple paths of UV light in
order to eliminate the impact of turbidity in the measurement.
The difference between the emitted radiation by the source
and the received radiation is proportional to the concentration
of monochloramine that is related to ammonia concentration.
AMMonIA In gAses
The measurement of ammonia in gases is very important in
many industries. Some clear examples are as follows:
• Ammonia production plants: to control the quality of
the final products and efficiency of the plant.
• Emission monitoring systems: some countries have
legislated ammonia emissions to the atmosphere.
• SNCR (Selective Noncatalytic Reductions): used in
combustion boilers for the measurement of the effi-
ciency of SCR units.
• Gas analysis: to verify the quality and composi-
tion of a gas. Currently, ammonia in gases is mea-
sured using several methods such as:
• NIR spectrophotometry. This method is used in
ammonia plants and emissions monitoring sys-
tems. They are often included in analyzer shelters
with other analyzers for emissions monitoring.
For more information see Chapter 1.32.
• Mass spectrophotometer. This method is used in
ammonia plants to control the quality of the pro-
duction. It is a versatile solution with the same
analyzer being used to control many parts of the
process. For more information see Chapter 1.35.
• Tunable diode laser (TDL). This is normally used
for NH3 control when found along with others com-
pounds (CO, CO2, etc.) in selective catalytic reduc-
tion units (SCR). These analyzers can be either
open path systems or in extractive arrangements,
the extractive type being the more expensive.
 1.5 Ammonia Analyzers 113

tunABle dIode lAser (tdl)

The TDL is an optical method that uses a laser to produce

a specific wavelength of light tuned to a specific absorption
line, the one corresponding to the light frequency of the
target gas. This laser radiation stimulates the vibration and
rotation in the gas molecules resulting in energy absorp-
tion. The principles used are the same as in the rest of the
photometers (UV, IR). The concentration is directly pro-
portional to the difference between the wavelengths of the
emitted and received radiations.
The main difference between the TDL and other pho-
tometers (UV and IR) is that the TDL can be used mounted
directly on equipment while the UV and IR photometers
(see Chapters 1.32 and 1.69) are extractive types. Another
difference is that the TDL has a greater precision than the
UV or IR photometers.
YOKOGAWA
In industry, two types of designs can be used for tunable
diode lasers. These are as follows:
Fig. 1.5f
• Open path TDL (Figure 1.5e). The open path system Extractive TDL for stack applications. (Courtesy of Yokogawa.)
is installed in situ (in the stream) and it is generally
used to measure gases in either cross-stack or off- • Extractive TDL (Figure 1.5f). The other major branch
gas (atmospheric vent) applications. Cross-stack use of TDL absorption spectroscopy is the extractive tech-
is commonly applied to flue gas stacks to measure nology, or online/at-line approach. This technology
contaminants contained in gases emitted from a fur- samples gases extracted from a stream into a compact
nace or a boiler. Some examples of off-gas applica- tubular chamber with mirrors. The mirrors reflect
tions include the measurement of gases at the exhaust an incoming laser beam, between 1 and 100 times,
of furnaces, ducts, or stacks. These types of emission before exiting the cell located inside the chamber.
measurements are commonly referred to as continu- Typical cell diameters vary from 25 to 75 mm, and
ous emissions monitoring systems (CEMS). CEMS their length can be from 100 to 500 mm. Due to its
analyzers monitor hazardous and prohibited contami- compact design, the extractive TDL analyzers offer
nants such as NOx. Another type of open path TDL is several advantages. They are small enough to permit
used to measure gas emissions across long distances convenient installation anywhere in a plant. The long
(approximately 500 m). This type can be used to mea- optical path of the cell enables high sensitive measure-
sure ammonia and CH4 emissions of livestock. ments of trace gases in small volumes. Measurements
of contaminants such as H 2S, and ammonia detect-
ing concentrations as ppm and ppb levels. Because
they operate outside the stream being measured, the
extractive TDL is not subject to particulate matter in
the flowing stream.

The main application of TDL in NH3 measurements is

emissions monitoring. When the required measurement must
be very accurate and the concentration to be measured is very
low, the extractive method is required (normally between 0
and 5 ppm). However, if the concentration is in the range of
0–5000 ppm, open path systems are normally used.

ConClusIon

The method of measurement of ammonium depends on

the state of the fluid, the range needed, and the accuracy
Fig. 1.5e required. The method must be revised according the mea-
Open patch TDL for stack applications. (Courtesy of Yokogawa.) surement requirement to perform.
114 Analytical Measurement

sPeCIfICAtIon forMs
When specifying ammonia analyzers only, please use the ISA
form 20A1001, and when specifying both the analyzer and
the composition or the properties of the process material of
interest, use ISA form 20A1002. The following are the forms
that reproduced with the permission of the International
Society of Automation.

1 RESPONSIBLE ORGANIZATION ANALYSIS DEVICE 6 SPECIFICATION IDENTIFICATIONS

2 7 Document no
3 Operating Parameters 8 Latest revision Date
4 9 Issue status
5 10
11 ADMINISTRATIVE IDENTIFICATIONS 40 SERVICE IDENTIFICATIONS Continued
12 Project number Sub project no 41 Return conn matl type
13 Project 42 Inline hazardous area cl Div/Zon Group
14 Enterprise 43 Inline area min ign temp Temp ident number
15 Site 44 Remote hazardous area cl Div/Zon Group
16 Area Cell Unit 45 Remote area min ign temp Temp ident number
17 46
18 SERVICE IDENTIFICATIONS 47
19 Tag no/Functional ident 48 COMPONENT DESIGN CRITERIA
20 Related equipment 49 Component type
21 Service 50 Component style
22 51 Output signal type
23 P&ID/Reference dwg 52 Characteristic curve
24 Process line/nozzle no 53 Compensation style
25 Process conn pipe spec 54 Type of protection
26 Process conn nominal size Rating 55 Criticality code
27 Process conn termn type Style 56 Max EMI susceptibility Ref
28 Process conn schedule no Wall thickness 57 Max temperature effect Ref
29 Process connection length 58 Max sample time lag
30 Process line matl type 59 Max response time
31 Fast loop line number 60 Min required accuracy Ref
32 Fast loop pipe spec 61 Avail nom power supply Number wires
33 Fast loop conn nom size Rating 62 Calibration method
34 Fast loop conn termn type Style 63 Testing/Listing agency
35 Fast loop schedule no Wall thickness 64 Test requirements
36 Fast loop estimated lg 65 Supply loss failure mode
37 Fast loop material type 66 Signal loss failure mode
38 Return conn nominal size Rating 67
39 Return conn termn type Style 68
69 PROCESS VARIABLES MATERIAL FLOW CONDITIONS 101 PROCESS DESIGN CONDITIONS
70 Flow Case Identification Units 102 Minimum Maximum Units
71 Process pressure 103
72 Process temperature 104
73 Process phase type 105
74 Process liquid actl flow 106
75 Process vapor actl flow 107
76 Process vapor std flow 108
77 Process liquid density 109
78 Process vapor density 110
79 Process liquid viscosity 111
80 Sample return pressure 112
81 Sample vent/drain press 113
82 Sample temperature 114
83 Sample phase type 115
84 Fast loop liq actl flow 116
85 Fast loop vapor actl flow 117
86 Fast loop vapor std flow 118
87 Fast loop vapor density 119
88 Conductivity/Resistivity 120
89 pH/ORP 121
90 RH/Dewpoint 122
91 Turbidity/Opacity 123
92 Dissolved oxygen 124
93 Corrosivity 125
94 Particle size 126
95 127
96 CALCULATED VARIABLES 128
97 Sample lag time 129
98 Process fluid velocity 130
99 Wake/natural freq ratio 131
100 132
133 MATERIAL PROPERTIES 137 MATERIAL PROPERTIES Continued
134 Name 138 NFPA h ealth hazard Flammability Reactivity
135 Density at ref temp At 139
136 140
Rev Date Revision Description By Appv1 Appv2 Appv3 REMARKS

Form: 20A1001 Rev 0 © 2004 ISA

 1.5 Ammonia Analyzers 115

1 RESPONSIBLE ORGANIZATION ANALYSIS DEVICE 6 SPECIFICATION IDENTIFICATIONS

2 COMPOSITION OR PROPERTY 7 Document no
3 Operating Parameters (Continued) 8 Latest revision Date
4 9 Issue status
5 10
11 PROCESS COMPOSITION OR PROPERTY MEASUREMENT DESIGN CONDITIONS
12 Component/Property Name Normal Units Minimum Units Maximum Units Repeatability
13
14
15
16
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18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
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35
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Rev Date Revision Description By Appv1 Appv2 Appv3 REMARKS

Form: 20A1002 Rev 0 © 2004 ISA

116 Analytical Measurement

Abbreviations Bibliography

CEMS Continuous emissions monitoring system ABB. Ammonium analyzer catalog (http://www.abb.com/product/
FFT Fast Fournier transform us/9AAC100044.aspx).
NaOCl Sodium hypochlorite American Society for Testing and Materials. 1979. Method
1426–79. American Society fo Testing & Materials,
NaOH Sodium hydroxide
Philadelphia, PA.
NH3 Ammonia ITA Publications. 2001. Online ammonia analyzers for water and
NH4Cl Ammonium chloride wastewater treatment applications. (http://www.instrument.
NIR Near infrared org/ePubs/site_map.htm).
SNCR Selective non-catalytic reductions U.S. Environmental Protection Agency. 1979. Methods for chemi-
TDL Tunable diode laser cal analysis of water and wastes. EPA-600/4-79-020, National
UV Ultraviolet Environmental Research Center, Cincinnati, OH.