A suitable calibration procedure for determination of N in fertilizers
by HR-CS FAAS should not be dependent on the type of N species present
in the sample. The influence of the nature of the N present on the capacity
of the flame to produce NO was therefore evaluated using
working standard solutions prepared using sodium nitrate, ammonium
chloride, and urea. The relationships obtained between absorbance and
the concentrations of the standard solutions are depicted in Fig. 1. All
the standards produced NO, and the higher the standard concentration,
the greater the NO absorbance. The conversion rate increased in the following
order: urea b ammonium b nitrate (Fig. 1a). The conversion of
ammonium and nitrate species into NO was similar for nitrogen stan-
dard solutions at concentrations up to around 2000 mg L
higher concentrations favored the formation of NO from nitrate, because
this species contains both nitrogen and oxygen and hence provides
a better N:O ratio, compared to ammonium. The decomposition
of urea can produce ammonium cyanate (NH
NCO), cyanic acid (HNCO), and ammonia [18], so the lower absorbances observed for
the urea standards could therefore be explained by the presence of stable
CN and CO bonds with energies of around 891 and 745 kJ mol 4,respectively
[19]. This means that a relatively long residence time of urea
in the flame is required in order to break these bonds and allow the recombination
reaction between N and reactive oxygen species to form
NO. The lower bond energy of NH (391 kJ mol−1) [19] provides an explanation
for the higher measured absorbance of NO obtained from ammonium,
compared to urea. Considering that the formation of NO is
favored by an excess of oxygen (more than is usually needed to burn
the fuel), evaluation was made of the influence of the addition of H
to the standards in order to assist the conversion to NO. Calibration
curves were constructed using nitrate, ammonium, and urea working
standards (500–10,000 mg L hydrogen peroxide.−1−1. However,N) in the presence of 0–10% (v/v) of
−12O2 Fig. 1. Calibration curves using nitrate (■), ammonium (●), and urea (▲) working standards (500–10,000 mg L The addition of 2.5% (v/v) H2O favored NO formation from all the test compounds, and similar slopes of the curves were obtained.However, the precision of the measurements made using urea was relatively low (RSD = 17%), compared to those conducted using nitrate (RSD = 3.3%) and ammonium (RSD = 3.5%). When the H2 concentration
was increased to 5% (v/v), the formation rate of NO also increased,
especially for the urea and ammonium standards (Fig. 1b).Under these conditions, the slopes of the curves obtained using nitrate,ammonium, and urea were similar (2.36 × 10−52O,2.32×10,and
2.31 × 10−5, respectively). The corresponding RSD values were 3.8,4.8, and 2.1%, respectively. Subsequent experiments were then carried out preparing blanks, working standard solutions, and sample extracts in 5% (v/v) H2O. It should be noted that NPK fertilizers containing
organic matter must be not analyzed unless a previous treatment is performed,because the presence of easily oxidized compounds can alter the hydrogen peroxide concentration and cause fluctuations in the NO signal.
A suitable calibration procedure for determination of N in fertilizersby HR-CS FAAS should not be dependent on the type of N species presentin the sample. The influence of the nature of the N present on the capacityof the flame to produce NO was therefore evaluated usingworking standard solutions prepared using sodium nitrate, ammoniumchloride, and urea. The relationships obtained between absorbance andthe concentrations of the standard solutions are depicted in Fig. 1. Allthe standards produced NO, and the higher the standard concentration,the greater the NO absorbance. The conversion rate increased in the followingorder: urea b ammonium b nitrate (Fig. 1a). The conversion ofammonium and nitrate species into NO was similar for nitrogen stan-dard solutions at concentrations up to around 2000 mg Lhigher concentrations favored the formation of NO from nitrate, becausethis species contains both nitrogen and oxygen and hence providesa better N:O ratio, compared to ammonium. The decompositionof urea can produce ammonium cyanate (NHNCO), cyanic acid (HNCO), and ammonia [18], so the lower absorbances observed forthe urea standards could therefore be explained by the presence of stableCN and CO bonds with energies of around 891 and 745 kJ mol 4,respectively[19]. This means that a relatively long residence time of ureain the flame is required in order to break these bonds and allow the recombinationreaction between N and reactive oxygen species to formNO. The lower bond energy of NH (391 kJ mol−1) [19] provides an explanationfor the higher measured absorbance of NO obtained from ammonium,compared to urea. Considering that the formation of NO isfavored by an excess of oxygen (more than is usually needed to burnthe fuel), evaluation was made of the influence of the addition of Hto the standards in order to assist the conversion to NO. Calibrationcurves were constructed using nitrate, ammonium, and urea workingstandards (500–10,000 mg L hydrogen peroxide.−1−1. However,N) in the presence of 0–10% (v/v) of−12O2 Fig. 1. Calibration curves using nitrate (■), ammonium (●), and urea (▲) working standards (500–10,000 mg L The addition of 2.5% (v/v) H2O favored NO formation from all the test compounds, and similar slopes of the curves were obtained.However, the precision of the measurements made using urea was relatively low (RSD = 17%), compared to those conducted using nitrate (RSD = 3.3%) and ammonium (RSD = 3.5%). When the H2 concentrationwas increased to 5% (v/v), the formation rate of NO also increased,especially for the urea and ammonium standards (Fig. 1b).Under these conditions, the slopes of the curves obtained using nitrate,ammonium, and urea were similar (2.36 × 10−52O,2.32×10,and2.31 × 10−5, respectively). The corresponding RSD values were 3.8,4.8, and 2.1%, respectively. Subsequent experiments were then carried out preparing blanks, working standard solutions, and sample extracts in 5% (v/v) H2O. It should be noted that NPK fertilizers containingorganic matter must be not analyzed unless a previous treatment is performed,because the presence of easily oxidized compounds can alter the hydrogen peroxide concentration and cause fluctuations in the NO signal.
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