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ISAMSE 2021 IOP Publishing
Journal of Physics: Conference Series 2021 (2021) 012072 doi:10.1088/1742-6596/2021/1/012072

Study on the Method of Measuring Nitrocellulose Nitrogen

Content

Yiying Zheng1, Heng Gao1, Xiang Cao1, Binbin Wang1, Fengqiang Nan1*
1
Nanjing University of Science and Technology, Nanjing
*Corresponding author’s e-mail: nanfq@njust.edu.cn

Abstract. The traditional five-tube nitrogen meter method, Dewald alloy method and the new
infrared spectroscopy, polarized light microscope method and other methods are briefly
introduced. The advantages and disadvantages of these detection methods are analyzed, and the
method for detecting the nitrogen content of nitrocellulose was prospected.

1. Introduction
Nitrocellulose is a compound produced by the reaction of nitric acid and cotton fiber, and the nitro
group replaces the hydrogen on the hydroxyl group of the cellulose molecule. It is a nitrate ester of
polyhydric alcohol. This reaction is essentially an esterification reaction. The degree of esterification
of cellulose by nitric acid can be expressed by three methods: percentage of nitrogen content, degree
of nitrification, and degree of esterification. The nitrogen content of nitrocellulose expressed by the
above three methods only represents how many grams of nitrogen are contained in a weight of
nitrocellulose, or how many hydroxyl groups are esterified in total, which is a statistical average value.
Nitrogen content is a very important technical indicator of nitrocellulose, which determines the energy
level and quality of nitrocellulose. Nitrogen content has a great influence on its physical and chemical
properties (such as solubility, viscosity and stability.) [1]. In general, nitrocellulose is used for
different purposes in accordance with the level of nitrogen content. Nitrocellulose with a nitrogen
content of less than 12.5% is mainly used as raw materials for daily products, such as coatings, inks,
plastics and other fields. Nitrocellulose with a nitrogen content of more than 12.5% plays an important
role in rocket propellants, propellants and explosives[2, 3] .
At present, there are many standard methods for determining the nitrogen content of nitrocellulose
in our country, from the past five-tube nitrogen meter method (referred to as the five-tube method) to
the Dewald alloy reduction method (referred to as the alloy reduction method), interferometer method,
etc. In recent years, some new detection methods have emerged, such as ferrous sulfate,
chromatography, infrared spectroscopy[4, 5, 6, 7]. Whether the nitrogen content of nitrocellulose can
be quickly and accurately determined is related to the long-term stability and production of military
and civilian nitrocellulose quality, performance measurement, and the development of new processes
and new methods. It has become an important means to ensure the quality of nitrocellulose.
The traditional five-tube nitrogen meter method, Dewald alloy method and the new infrared
spectroscopy, polarized light microscope method and other methods are briefly introduced, the
advantages and disadvantages of these detection methods are analyzed, and the method for detecting
the nitrogen content of nitrocellulose was prospected.

Content from this work may be used under the terms of the Creative Commons Attribution 3.0 licence. Any further distribution
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ISAMSE 2021 IOP Publishing
Journal of Physics: Conference Series 2021 (2021) 012072 doi:10.1088/1742-6596/2021/1/012072

2. Nitrocellulose Nitrogen Content Testing Method

2.1 Five-tube nitrogen meter method

The five-tube method uses concentrated sulfuric acid to decompose the sample into nitric acid, and
then converts the nitrogen content of the sample by measuring the volume of nitrogen oxide generated
after the reduction of metal mercury. The five-tube nitrogen meter method is widely used and has high
measurement accuracy. However, this method has a flaw, which is serious toxicity. From the
preparation stage, the reaction stage, to the measurement and washing process, the analyst cannot
avoid facing a large amount of mercury vapor, and mercury is extremely harmful to the human body.
The five-pipe method has seasonal fluctuations, with low results in summer and high results in winter,
and the operation is complicated. Therefore, this method is not suitable for mass determination, and is
only used when arbitration is required.

2.2 Dewald alloy reduction method

The alloy reduction method is to measure the nitrate ester group in nitrocellulose by the volumetric
analysis method. It has a wide range of applications and can determine the content of various
nitrocellulose, nitrates, etc. The alloy reduction method is to saponify nitrocellulose with lye to
produce nitrate under the condition of hydrogen peroxide, reduce it to ammonia with Dewald alloy,
and absorb it with boric acid, titrate with hydrochloric acid standard solution, and measure the
nitrogen content in nitrocellulose. Its operation difficulty is not as high as the five-pipe method, the
result is high in accuracy, the influencing factors are easy to overcome, and the working conditions are
greatly improved compared with the five-pipe method. However, its operating procedures are
complicated and difficult to master.
Liu Hongni [8] et al. used a convenient method of saponification of nitrocellulose based on the
principle of Dewald alloy reduction reaction, and realized the determination of nitrogen content in
nitrocellulose through a self-developed automatic nitrogen analyzer. The saponification of
nitrocellulose in the automatic nitrogen analyzer adopts the method of graphite furnace heating, so that
the nitrocellulose sample can be evenly heated, avoiding the side decomposition reaction caused by
local overheating in the traditional method of electric furnace heating, so as to ensure the consistency
of the operation process. The automatic nitrogen analyzer method is used to determine the nitrogen
content of nitrocellulose, the data is accurate and reliable, and the equipment has a high degree of
automation, which can greatly improve work efficiency.

2.3 Interferometer method

This is an analysis method commonly used in factories now. After nitrocellulose deflagrates in a
closed state, the main gases produced are carbon monoxide, carbon dioxide, hydrogen, nitrogen and
water vapor, in addition to trace amounts of methane and other gases. The percentage of these gas
components is closely related to the nitrification degree of nitrocellulose. When the degree of
nitrification of nitrocellulose is high, the number of nitrate ester groups in the long chain of its
macromolecule is more, that is, it contains more nitrogen and oxygen atoms. This will not only
increase the percentage of nitrogen in the gas components after combustion, but also increase the
amount of carbon dioxide and water produced due to the higher oxygen content. The production of
methane and other trace gases is also related to the composition and deflagration temperature of
nitrocellulose.The composition of the gas after deflagration is different, which causes a slight
difference in the refractive index of the mixed gas. The gas after deflagration is introduced into the
interferometer, and its relative refractive index difference is measured, thereby converting the nitrogen
content of the nitrocellulose. This method is fast, simple and accurate, and avoids mercury poisoning,
so it has been widely promoted. However, it is still the same as many other instrumental analysis
methods. It must be compared with the chemical method-the five-tube method, and can be used after
drawing a reference curve. Also, different sources of nitrocellulose need to be drawn with different
curves, which is a major disadvantage of it.

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ISAMSE 2021 IOP Publishing
Journal of Physics: Conference Series 2021 (2021) 012072 doi:10.1088/1742-6596/2021/1/012072

2.4 Ferrous-titanium chloride method

Nitrocellulose is oxidized and reduced with ferrous ammonium sulfate solution under the protection of
inert gas and then titrated with titanium chloride standard solution to calculate the nitrogen content of
nitrocellulose. The instrument used in this method is complicated and the operation is complicated,
requiring a lot of practice to accurately measure.

2.5 Salicylic acid-subtitanium method

The nitrate ester group of nitrocellulose can generate nitrosalicylic acid from salicylic acid in sulfuric
acid solution, which is reduced to aminosalicylic acid with titanite (such as titanium trichloride), and
the remaining titanite is ferric ammonia sulfate standard solution Perform titration. However, this
method is difficult to master, and the price of subtitanium salt is relatively expensive, which is not
suitable for mass production.

2.6 Chromatography
Analyst place the nitrocellulose in a closed container, and after deflagration, measure the peak height
of certain components in the fuel gas or the ratio of the peak heights between the components by
chromatography. This method was used to determine the nitrogen content of No.3 nitrocellulose.
However, this method has major shortcomings, that is, the sample processing time is long, and the
instrument is large and expensive, so it is not convenient to be applied in online testing.

2.7 Caloric method

The heat of nitrocellulose is closely related to its degree of nitrification. The measurement of the heat
of nitrocellulose is converted into the degree of nitrification. Various factories have done a lot of
experiments. Although this method can protect the operator from the poison of mercury vapor, the
working hours are not short and the operation is more complicated. Nitrocellulose produced in
different factories requires different conversion formulas, so it is not officially used in production.

2.8 Elemental analyzer method

In 1997, Liu Xiaohui [9] and others established a new nitrogen analysis method to analyze the
nitrogen content of nitrocellulose in single-base drugs. This method uses the principle of reactive gas
chromatography, that is, under the condition of high temperature (1020℃), the compound
(nitrocellulose) is combusted under the action of oxidant (Cr2O3), and the nitrogen, carbon, hydrogen
and other elements contained in it are quantitatively Converted into nitrogen oxides, carbon dioxide
and water. Nitrogen and oxygen compounds are reduced by copper and converted into nitrogen; the
absorption tube absorbs moisture; after nitrogen and carbon dioxide are separated by the
chromatographic column and detected by the thermal conductivity cell, the mass fraction of nitrogen is
calculated by the NA-1500 nitrogen analyzer. They also conducted comparative experiments with the
five-tube method and the interferometer method, and the results showed that the elemental analysis
method is a good method to determine the nitrogen content of nitrocellulose.
In 2002, Li Shuxing [10] et al. reported the analysis of the nitrogen content of nitrocellulose in a
single-base medicine also with the NA-1500 element analyzer produced by an Italian company. They
selected five commonly used single-base drug samples and used the nitrogen analyzer method and the
interferometer method for comparative analysis to determine the nitrogen content of the nitrocellulose.
The difference between the parallel results of this method was less than 0.3, and the measured results
were average. The value is compared with the measurement result of the interferometer method, the
range is 0.27, which is less than the system error of the nitrogen analyzer.
In 2013, Liu Hongni [11] and others used the Vario MACRO cube element analyzer to measure the
nitrogen content of nitrocellulose. This analyzer is a large injection volume element analyzer launched
by German Elementar in 2009 for samples with poor uniformity or low content.They optimized the
experimental determination conditions, established a method for determining the nitrogen content of

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ISAMSE 2021 IOP Publishing
Journal of Physics: Conference Series 2021 (2021) 012072 doi:10.1088/1742-6596/2021/1/012072

nitrocellulose, and achieved satisfactory results. The precision of this method is 0.21%～0.37%, and
the recovery rate is 99.16%～100.31%.
In 2015, Wei Han [12] and others established a new analytical method to analyze the nitrogen
content of nitrocellulose in gunpowder. After pretreatment of the gunpowder sample, the NC-2000
nitrogen element analyzer was used to directly measure nitrogen. The five typical grades of
gunpowder were measured. The nitrogen element analyzer and the five-tube method were used for
comparison. The relative standard deviation was < 1.89%, the recovery rate is 98.52%~100.34%, the
result is satisfactory.
The elemental analyzer method has high degree of automation, easy operation, high precision and
accuracy, and is non-toxic and safe. It is a good choice for determining the nitrogen content of
nitrocellulose.

2.9 Kjeldahl nitrogen determination method

The sample is nitrated with concentrated sulfuric acid under the condition of a catalyst, so that organic
nitrogen is converted into inorganic ammonium salt, and then the ammonium salt is converted into
ammonia under alkaline conditions, which is distilled out with steam and absorbed by excess boric
acid solution. Standard hydrochloric acid titration to calculate the nitrogen content of nitrocellulose.
When using this method to determine the nitrogen content, often due to the added catalyst is too little
or the reducibility is too weak, the very small amount of nitrogen in the nitro group is reduced to
amino groups, and most of the nitrogen is reduced to nitrogen or nitrogen low-valent oxides, causing
the measured nitrogen content to be lower than the standard value. Therefore, when analyzing the
nitrogen content of nitrocellulose, more catalysts with strong reducing properties should be added to
ensure the accuracy of the results.

2.10 Infrared spectroscopy method

Wen Xiaoyan [13]and others established a mathematical model for determining the nitrogen content of
nitrocellulose using near-infrared diffuse reflectance spectroscopy. This model has high accuracy and
precision,and when the significance level is 0.05, there is no significant difference between the value
predicted by the near-infrared spectroscopy and the chemical analysis value. Therefore, this method
can replace the chemical analysis method to analyze the nitrogen content of nitrocellulose. The
disadvantage is that the infrared spectroscopy instrument is large in size, so it is not suitable for online
detection.

2.11 Polarized light microscopy method

Under a positive polarized light microscope, when linearly polarized light enters the nitrocellulose
fiber sample, the optical path difference will be generated due to birefringence, and after passing
through the microscope, polarized light will interfere and present a polarized color. The nitrogen
content of nitrocellulose has a linear relationship with the optical path difference, and the optical path
difference corresponds to the polarized light color one by one. Therefore, the mathematical
relationship between the nitrogen content and the optical path difference can be established based on
the change of the polarized color of the nitrocellulose with known nitrogen content, so that the
nitrogen content of the unknown sample can be obtained.
Su Pengfei [14] et al. used the Senamon method to determine the average optical path difference.
The results show that when the nitrogen content of nitrocellulose is 11.0%～13.8%, the optical path
difference is linearly related to the nitrogen content. The test results of the new method were verified
with nitrocellulose standard materials, the recovery rate was 99.7%～100.2%, and the coefficient of
variation was 0.15%～0.20%.The method can also be used to evaluate the uniformity of nitrocellulose
nitrification, and has the advantages of simple detection device, no damage to materials, simple
operation, accurate results and environmental friendliness.

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ISAMSE 2021 IOP Publishing
Journal of Physics: Conference Series 2021 (2021) 012072 doi:10.1088/1742-6596/2021/1/012072

2.12 Capillary Electrophoresis method (CE)

The driving force of capillary electrophoresis is a high-voltage direct current electric field, and the
separation channel is a capillary. The separation and analysis are realized based on the difference in
mobility and distribution behavior of the components in the sample. It is a new type of liquid phase
separation and analysis technology.
Elodie Alinat [15] et al. hydrolyzed nitrocellulose separated from living materials and propellant
with alkali, and studied the influence of hydrolysis time and the molar mass of nitrocellulose on the
molar ratio of nitrite and nitrate. Because there is a linear relationship between the nitrogen content
and the molar ratio of nitrite to nitrate, the ratio of nitrite to nitrate can be measured by establishing a
calibration curve of a standard nitrocellulose standard to determine the nitrogen content of
nitrocellulose in real samples. This method is suitable for the determination of the nitrogen content of
nitrocellulose in living materials and energetic materials. The relative standard deviation of the
measured nitrogen content (n=3)<1.5%. The advantages of this method are high accuracy, less time-
consuming, and convenient operation.

3. Conclusion
The nitrogen content of nitrocellulose determines the stability and energy of nitrocellulose. Therefore,
finding and determining a suitable nitrocellulose nitrogen content detection method is very important
to ensure the production quality of nitrocellulose. This detection method must meet the conditions of
convenience, speed and accuracy. In the past, traditional detection methods could not meet the above
conditions at the same time. Like table 1 shows, most of the methods have the disadvantage of
cumbersome operation, such as five-tube nitrogen meter method, alloy reduction method, ferrous-
titanium chloride method, salicylic acid-titanium method and calorie method. In recent years, some
new detection methods have come out, such as chromatography and infrared spectroscopy.However,
the Kjeldahl nitrogen determination method is limited by its own detection principle, and the accuracy
cannot be guaranteed. The detection instruments of chromatography and infrared spectroscopy are too
large to be able to perform online or large-scale measurement.
Table 1 Defects of nitrogen content of nitrocellulose
Conditions to be met
detection method
convenient fast accuracy
Five-tube nitrogen meter method ×
Dewald alloy reduction method ×
Ferrous-titanium chloride method ×
Salicylic acid-subtitanium method ×
Chromatography × ×
Caloric method × ×
Kjeldahl nitrogen determination method ×
Infrared spectroscopy method × ×

In order to overcome these shortcomings, researchers have made many attempts. Some researchers
have improved the alloy reduction method and developed an automatic nitrogen determination
instrument. Others have also found new methods such as polarized light microscopy method and
capillary electrophoresis method to measure the nitrogen content of nitrocellulose. These efforts have
achieved certain results. The automatic nitrogen analyzer has a high degree of automation, which can
greatly improve work efficiency. And new methods such as polarized light microscopy method and
capillary electrophoresis method have the advantages of high automation, less time-consuming
detection, simple and convenient operation, low toxicity, and high accuracy, which are worthy of
popularization and application. In future research, the following aspects can be used to promote the
further development of nitrocellulose nitrogen content detection methods.

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ISAMSE 2021 IOP Publishing
Journal of Physics: Conference Series 2021 (2021) 012072 doi:10.1088/1742-6596/2021/1/012072

One is to improve traditional methods. Through the targeted improvement of traditional methods,
the shortcomings of traditional nitrocellulose nitrogen content detection methods are avoided, and its
application is more extensive. The other is to find new ways. By finding the quantitative influence
relationship of the nitrogen content of nitrocellulose on the physical properties of nitrocellulose, the
nitrogen content of nitrocellulose was determined. So that the theoretical method can be applied to a
wide range of practice

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