Trace Analysis of Ammonia

in Ethylene by Gas Chromatography

and Nitrogen Chemiluminescence
Detection

Application Note
Energy & Chemicals, Polymers

Author Abstract
Kelly Beard A gas chromatography method was developed for the measurement of trace
Agilent Technologies, Inc. ammonia in ethylene by capillary gas chromatography (GC) and nitrogen
chemiluminescence detection. This method determined the concentrations of
ammonia in the parts per billion volume (ppbv) to parts per million volume (ppmv)
range. Due to the reactivity problems associated with ammonia, the discussion
focuses on low-level linearity and precision.
Introduction Experimental (Valve 1) was switched on to inject
sample. After 0.25 minutes, Valve 1
The measurement of trace ammonia in The instrument consists of an
was switched off. During the analysis,
ethylene is important in the production Agilent 7890B GC configured with an
the oxidizer flow was set to remain at
of polymers and other petroleum-based Agilent 8255 NCD, and a 6-port gas
the maximum flow of 30 mL/min. The
chemical products. To reach the sub‑parts sample valve. The gas sample valve uses
high oxidizer flow prevents catalyst
per million volume (ppmv) detection limits a 1‑mL gas sample loop, directly injected
coking when the matrix hydrocarbons
required for this industry, the use of a on a megabore column, (p/n CP8590,
pass through the detector. Just before
nitrogen chemiluminescence detector Select Low Ammonia). All sample-wetted
ammonia eluted to the detector, the
(NCD) is required. In the past, NCDs surfaces were stainless steel deactivated
oxidizer flow was automatically set to
have experienced coking on the internal with an Agilent UltiMetal Plus treatment.
4 mL/min. This allowed the ammonia
catalyst tube due to high‑concentration Instrument control, data acquisition, and
to be analyzed under optimum flow
hydrocarbon matrices. Over time, this data analysis were performed using the
conditions. After ammonia elution,
caused a decrease in detector response. Agilent OpenLAB CDS data system.
the high 30 mL/min oxidized flow was
As a result, complex valve configurations
The ammonia analysis procedure began re-established to prevent further coke
were necessary to either vent the
by purging the sample loop with standard formation. Figure 1 shows an example
hydrocarbon matrix so it did not reach the
or sample. After the sample introduction chromatogram.
detector, or increase the oxidizer gas to
the detector to decoke the catalyst tube. purge, the 6-port gas sample valve
The Agilent 8255 NCD uses electronic
pressure control (EPC), giving it the ability
to automatically adjust the oxidizer flow Chromatographic conditions
rate, and decoke without the use of a Temperatures
complex valve system. This Application
Note discusses a fast and simple GC Valve/valve box 125 °C
configuration to analyze ammonia gas to Column oven 100 °C (hold 0.25 minutes), ramp 25 °C/min to 150 °C (hold 2.75 minutes)
low parts per billion volume (ppbv) levels NCD Base 200 °C
in light hydrocarbons. NCD Burner 900 °C
Flows
Column 1 10 mL/min
NCD Oxidizer flow 30 mL/min
NCD Hydrogen flow Off
Valve timing
Valve 1 (6-port) On at 0.01 minutes, off at 0.25 minutes

×101
Ammonia
1.0
1.958
0.95
0.9
0.85 Ethylene
disruption
0.8
0.75
Response (pA)

0.7
0.65
0.6
0.55
0.5
0.45
0.4
0.35
0.3
Oxidizer flow set to 30 mL/min Oxidizer flow set to 4 mL/min Oxidizer flow set to 30 mL/min
0.25
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2 3.4 3.6 3.8 4.0 4.2 4.4 4.6 4.8
Retention time (min)

Figure 1. Example chromatogram, 50 ppbv ammonia.

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Results and Discussion ×106 Concentration
12 (ppbv) Area
Linearity 10 0 0

Area response
To establish an R2 value, trace level 8 50 1,279,093
R2 = 0.999
ammonia linearity was investigated by 6 100 2,547,019
analyzing four different concentrations, 4 200 4,927,718
with the addition of the origin. Figure 2 2 400 10,597,983
shows the results. The analysis resulted 0
0 50 100 150 200 250 300 350 400 450
in an R2 value of 0.999 from 50 to Concentration
400 ppbv, including the origin. A 500 ppbv
ammonia in ethylene gas standard with Figure 2. Ammonia linearity.
a dynamic dilution system was used to
generate the various concentration levels.
Ammonia Run Area
1 261.41
Precision 90
2 251.84
Precision was investigated by analyzing 3 269.22
six consecutive replicates of a 50 ppbv 80
4 272.67
standard to establish relative standard 5 262.20
Response (pA)

deviation (RSD). RSD was reported at 70 6 264.08

2.73 %. Figure 3 shows the results. Average 263.57
60 STD 7.20
Conclusion RSD 2.73 %

The Agilent 7890B GC configured with 50

the Agilent 8255 NCD provides a simple

and fast way to analyze trace ammonia in 40
light hydrocarbons. Automated changes
to the NCD oxidizer flow optimize 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0
ammonia response and reduce adverse Retention time (min)
matrix effects in the detector. Over time, Figure 3. Precision: ammonia 50 ppbv.
this technique maintains system uptime
by reducing maintenance. The approach
provides the sensitivity, reproducibility,
and linearity required for the hydrocarbon
industry. Note that performance
improvements can be obtained using all
UltiMetal Plus sample tubing including
regulators and fittings.

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This information is subject to change without notice.

© Agilent Technologies, Inc., 2017

Published in the USA, May 5, 2017
5991-8061EN