Analysis method of total nitrogen, phosphorus and potassium

content in Water soluble fertilizers

Analysis method of total nitrogen
1. Summary
In alkaline medium, nitrate is reduced by fixed nitrogen alloy and ammonia is
distilled directly. Or in the acidic medium to reduce nitrate into ammonium salt, in
the presence of mixed catalyst, with concentrated sulfuric acid digestion, organic
nitrogen or amide nitrogen into ammonium salt, ammonia distillation from the
alkaline solution. Ammonia was absorbed in excess sulfuric acid solution and
titrated back with sodium hydroxide standard titration solution in the presence of
methyl red and methylene blue mixed indicator to calculate the total nitrogen
content in the sample.
2. Reagents
Sulfuric acid.
Hydrochloric acid.
Absolute ethanol.
Selenium powder: fineness less than 250μm.
Chromium powder: fineness less than 250μm.
Potassium sulfate.
Copper sulfate pentahydrate.
Nitrogen alloy (Cu: 50%, A1:45%, Zn: 5%): fineness less than 850μm.
Mixed catalyst: carefully grind 1000g potassium sulfate and 50g copper sulfate
pentahydrate to pass through 0.25mm pore size test screen, add 1g selenium
powder and mix thoroughly.
Sodium hydroxide solution: ρ(NaOH)=400g/L.
Sodium hydroxide standard titration solution: C (NaOH)=0.5mol/L.
Sulfuric acid solution: C [1/2(H2SO4)]=0.5mol/L.
Methyl red-methylene blue mixed indicator: Weigh 0.10g methyl red and 0.05g
methylene blue, dissolve them with a small amount of absolute ethanol for several
 times, dilute them to 100mL and mix well.
Extensive pH test strips.
3. Apparatus
General laboratory instruments.
Porous digester with adjustable temperature within 400℃.
Automatic nitrogen distillation apparatus.
4. Procedure
4.1 Preparation of test solution
After the solid sample has been reduced for several times, about 100g is taken out,
which is quickly ground to pass through 0.50mm aperture sieve (if the sample is
wet, it can pass through 1.00mm sieve), mixed evenly, and placed in a clean and
dry container; After repeated shaking, about 100mL of the liquid sample was
quickly removed and placed in a clean, dry container.
4.2 Test solution processing and distillation
4.2.1 Samples containing only ammonium.
The sample with total chlorine content less than 235mg was weighed 0.5g~2g
(accurate to 0.0001g) in the digestion (distillation) tube, and about 70 mL water
was added, and the sample was shaken to dissolve.
Start the instrument according to the manual procedure of automatic fixed
ammonia distiller. Add 50.0mL sulfuric acid solution and 4 ~5 drops of mixed
indicator to a 500mL triangular flask, and place the flask on the ammonia
receiving tray of the distillation apparatus. Connect the digestion (distillation) tube
to the instrument distillation head, add 20mL of sodium hydroxide solution, and
start distillation. When the distillate reaches about 300mL, check the droplets at
the mouth of the ammonia liquid output tube with a pH test strip, and end the
distillation if it does not show alkalinity.
4.2.2 Samples containing ammonia nitrate and ammonium nitrogen.
The sample with total nitrogen content not more than 235mg and nitric nitrogen
content not more than 60mg was weighed 0.5g~2g(accurate to 0.0001g) in the
digestion (distillation) tube, and about 70mL water was added, then the sample
 was dissolved by shaking. 3g nitrogen alloy is added and the digestion (distillation)
tube is connected to the automatic nitrogen distillation apparatus at the ready.
The distillation process is the same as 4.2.1 except that 20mL of sodium
hydroxide solution is added and the distillation is allowed to stand for 10min
before starting.
4.2.3 Samples containing amide nitrogen and ammonium nitrogen.
The sample with the total nitrogen content less than 235mg was weighed 0.5g~ 2g
(accurate to 0.0001g) in the digestion (distillation) tube, 0.5g copper sulfate
pentahydrate and 10mL sulfuric acid were added, inserted into the long-necking
glass funnel, and placed on the digester. The temperature was adjusted to 380℃,
and the temperature was heated until the sulfuric acid turned white smoke for
20min. After the digestion (distillation) tube cools to room temperature, add about
70mL water.
The distillation process follows the same steps as 4.2.1 except adding 50mL
sodium hydroxide solution.
4.2.4 Samples containing organic matter, amide nitrogen and ammonium nitrogen.
The sample with the total nitrogen content less than 235mg was weighed
0.5g~2g(accurate to 0.0001g) in the digestion (distillation) tube, 2g mixed catalyst
and 10mL sulfuric acid were added, inserted into the long-necking glass funnel,
and placed on the digester. The temperature was adjusted to 380 ℃ , and the
sample solution was heated until it was colorless and transparent or grayish white.
Allow the digestion (distillation) tube to cool to room temperature before adding
about 70mL of water.
The distillation process is the same as 4.2.1 except that 50mL of sodium
hydroxide solution is added.
4.2.5 Samples containing nitric, amide and ammonium nitrogen.
The sample with total nitrogen content not more than 235mg and nitric nitrogen
content not more than 60mg was weighed 0.5g~2g(accurate to 0.0001g) in the
digestion (distillation) tube, and 10mL water was added, then the sample was
dissolved by shaking. Add 1.2g chromium powder and 7mL hydrochloric acid, let
 stand for 5min, and insert a long-necked glass funnel.
Place the digestion (distillation) tube on the digester, adjust its temperature to
100 ℃ , heat to boiling and produce a large amount of dark green foam, and
continue to heat for 2min~3min. After cooling to room temperature, 0.5g copper
sulfate pentahydrate and 10mL sulfuric acid were added, and the furnace
temperature was gradually raised to 380℃. The digestion (distillation) tube was
constantly shaken to ensure that the solution in the tube did not deposit and
agglomerate. After sulphuric acid is fumed for 20min, stop heating, and add about
70mL water when the digestion (distillation) tube cools to room temperature.
The distillation process follows the same steps as 4.2.1 except adding 60mL
sodium hydroxide solution.
4.2.6 Samples containing nitric nitrogen, organic matter, amide nitrogen and
ammonium nitrogen.
The sample with total helium content not more than 235mg and nitric nitrogen
content not more than 60mg was weighed 0.5g~2g (accurate to 0.0001g) in the
digestion (distillation) tube, and 10mL water was added, then the sample was
dissolved by shaking. Add 1.2g chromium powder and 7mL hydrochloric acid, let
stand for 5min, and insert a long-necked glass funnel.
Put the digestion (distillation) tube on the digester, adjust its temperature to 100℃,
heat to boiling and produce a large amount of dark green foam, continue to heat
for 2min~3min, cool to room temperature. Add 2g of mixed catalyst and 10mL
sulfuric acid, insert a long-necked glass funnel, and soak overnight. The next day,
the digestion (distillation) tube was placed on the dry digester, and the temperature
was gradually raised to sulfuric acid and smoke, and the digestion was carried out
at 380 ℃ . During digestion, the digestive tube should be constantly shaken to
ensure that the solution in the tube does not settle into clumps. After 60min of
digestion, the heating was stopped. After the digestion (distillation) tube was
cooled to room temperature, about 70mL water was added.
The distillation process is the same as 4.2.1 except that 60mL of sodium
hydroxide solution is added.
4.2.7 Titration of distilled solution.
The excess sulfuric acid was titrated back with sodium hydroxide standard
titration solution until the indicator appeared gray green as the endpoint.
4.3 Blank test
Except without the sample, the other steps are the same as the sample solution
determination.
5. Calculation
The content of total nitrogen, w, is expressed as %. It is calculated according to
equation (1):

(V1 -V2)c×0.01401
w = --------------------------× 100 (1)
m

Where:
c -- the concentration of sodium hydroxide standard titration solution used in the
sample and blank test, in moles per liter (mol/L);
V1-- Volume of sodium hydroxide standard titration solution, in milliliters (mL),
used in the determination of the sample;
V2-- volume of sodium hydroxide standard titration solution in milliliters (mL) for
the blank test;
0.01401-- mass of nitrogen in grams equivalent to 1.00mL of sodium hydroxide
standard titration solution [c (NaOH)=1.000mol/L], expressed in grams per
millimole (g/mmol);
m -- mass of the test material in grams (g).
6. Deviation
The deviation of the test results of two parallel tests in not more than 0.3%.
Analysis method of phosphorus
1. Summary
In the sample solution, orthophosphate ion and quinolybdate reagent in acidic
medium to produce yellow quinoline phosphomolybdate precipitation, the content
of phosphorus was determined by quinoline phosphomolybdate gravimetric
method.
2. Reagents
Nitric acid solution, C (HNO3) = 0.1mol/L.
Solution of nitric acid, 1 + 1.
Quinmolimone reagent: Solution A: Dissolve 70g ammonium molybdate in
100mL water; Solution B: Dissolve 60g citric acid in 100mL water and add 85mL
nitric acid; Solution C: under constant agitation, add solution A to solution B
slowly and mix well; Solution D: take 5mL quinoline and dissolve it in a mixture
of 35mL nitric acid and 100mL water. Under constant agitation, the solution D
was slowly added into solution C, mixed and placed in the dark overnight, filtered
with filter paper, and the filtrate was added into 280mL acetone, diluted to 1L with
water, shaken well, and stored in a polyethylene bottle, placed in the dark, away
from light and heat.
3. Apparatus
Glass Crucible filter: No. 4, volume 30 mL.
Electric constant temperature drying oven: the temperature can be controlled in
180 °C ±2 °C.
Common laboratory instruments.
4. Procedure
4.1 Preparation of test solution
After the solid sample has been reduced for several times, about 100g is taken out,
which is quickly ground to pass through 0.50mm aperture sieve (if the sample is
wet, it can pass through 1.00mm sieve), mixed evenly, and placed in a clean and
dry container; After repeated shaking, about 100mL of the liquid sample was
quickly removed and placed in a clean, dry container.
4.2 Preparation of sample solution
Weigh the sample containing P2O5 250mg~500mg 1g~ 4g (accurate to 0.0001g)
in 250mL volumetric bottle, add 50mL nitric acid solution, fully dissolve, constant
volume of water, dry filtration after mixing, discard the first few milliliters of
filtrate, filtrate to be tested.
4.3 Determination
Take 10.00ml sample solution, put it in a 500mL beaker, add 10mL nitric acid
solution, and dilute it to 100mL with water. Cover the surface dish and heat it to
boiling on an electric furnace. Remove the beaker and add 35mL
quinolymo-limone reagent. Cover the surface dish and boil it slightly on an
electric heating plate for 1min or place it in a near boiling water bath to keep it
warm until the precipitation is stratified.
The supernatant was filtered by a glass crucible filter which was dried to constant
weight in a drying oven at 180 ° C ±2 ° C in advance. Then the supernatant was
washed and precipitated by the pouring method for 1 ~2 times (about 25mL water
for each time). Transfer all the precipitate to the filter, filter dry and then wash the
precipitate with water for many times (the total water used is 125mL~150mL). Put
the precipitate together with the filter in the drying oven at 180 ° C ±2 ° C, wait
for the temperature to reach 180 ° C, dry for 45min, take out and transfer to the
dryer, cool to room temperature, and weigh.
4.4 Blank test
Except without the sample, the other steps are the same as the sample solution
determination.
5. Calculation
The content of phosphorus, w, is expressed as %. It is calculated according to
equation (2):

(m1 -m2)×250×0.03207 (m1 -m2)×250

w1 = --------------------------×100 = -------------------------- (2)
m × 10 m
 Where:
m1: mass of quinoline phosphomolybdate precipitate, in grams (g);
m2: mass of quinoline phosphomolybdate precipitate in grams (g) of blank test;
m: mass of the test material in grams (g);
250- volume of sample solution in milliliters (mL);
10- volume of sample solution separated, in milliliters (mL);
0.03207- quinoline phosphomolybdate mass conversion coefficient to phosphorus
pentoxide mass.
Conversion of mass concentration:
Liquid fertilizer phosphorus (P2O5) content ρ(P2O5), expressed as mass
concentration (g/L), calculated according to equation (3):
ρ(P2O5) = 10wρ (3)
Where:
w -- the mass fraction of phosphorus in the sample, expressed in percentage (%);
ρ-- density of the liquid sample in grams per milliliter (g/mL).
6. Deviation
The deviation of the test results of two parallel tests in not more than 0.3% and choose
the average value as the final result.
Analysis method of potassium
1. Summary
Potassium ions in sample solution were precipitated by sodium tetrabenylborate
solution in weakly alkaline medium, and potassium content was determined by
potassium tetrabenylborate gravimetric method. In order to prevent cation
interference, the appropriate amount of EDTA (ethylenediamine tetraacetic acid
disodium salt) can be added in advance, so that the cation and EDTA disodium
complexation.
2. Reagents
Ethylenediamine tetraacetic acid disodium salt solution: ρ(EDTA)=40g/L.
Sodium hydroxide solution: ρ(NaOH)=400g/L.
Magnesium chloride solution: ρ(MgCl2·6H2O)=100g/L.
Sodium tetraphenylborate solution: ρ[NaB(C6H5)4]=15g/L. Weigh 15g sodium
tetrabenylborate and dissolve it in about 960mL water, add 4mL sodium hydroxide
solution, stir well, then add 20mL magnesium chloride solution, stir for 5min,
stand for 24h, then filter with filter paper. The solution is stored in brown or
polyethylene bottles and stabilizes within a month. If found cloudy, should be
filtered before use.
Sodium tetraphenylborate detergent: ρ[NaB(C6H5)4]=1.5g/L. Dilute 1 volume of
sodium tetrabenylborate solution with 9 volumes of water.
Phenolphthalein solution: ρ(phenolphthalein)=5g/L, dissolve 0.5g phenolphthalein
in 100mL 95% ethanol.
3. Apparatus
Glass Crucible filter: No. 4, volume 30 mL.
Electric constant temperature drying oven: the temperature can be controlled in
120 °C ±2 °C.
Common laboratory instruments.
4. Procedure
4.1 Preparation of test solution
After the solid sample has been reduced for several times, about 100g is taken out
 and quickly ground to pass through the 0.50mm aperture sieve (if the sample is
wet, it can pass through the 1.00mm sieve), mixed evenly, and placed in a clean
and dry container; After repeated shaking, about 100mL of the liquid sample was
quickly removed and placed in a clean, dry container.
4.2 Preparation of sample solution
Solid sample:
The sample containing about 400mg of potassium oxide was weighed
1g~5g(accurate to 0.0001g), placed in a 400mL beaker, heated with about 150mL
water, boiled for 30min, cooled, transferred to a 250mL volumetric bottle, fixed
with water, mixed, filtered dry, discarded the first few milliliters of filtrate, and the
filtrate was to be tested.
Liquid sample:
Weigh 1g~10g of the sample containing about 400mg of potassium oxide
(accurate to 0.0001g) in a 250mL volumetric bottle, set the volume with water,
mix well, dry filter, discard the first few milliliters of filtrate, filtrate to be tested.
4.3 Determination
Absorb a certain volume of sample solution, put it in a 300mL beaker, add
40mLEDTA solution (containing too much cation can be added in an appropriate
amount), add 2 to 3 drops of phenolphthalein solution, add sodium hydroxide
solution until the red color appears, then excess 1mL, cover the surface dish. Boil
slowly in the fume hood for 15min, remove the beaker, rinse the surface dish with
a small amount of water, and cool to room temperature. If the red disappears,
adjust to red with sodium hydroxide solution. Under constant stirring, add sodium
tetrabenylborate solution, 1mg potassium oxide and 0.5ml sodium
tetrabenylborate solution to the sample solution drop by drop, and an excess of
about 7mL, continue stirring for 1min, and stand for 15min~30min.
The supernatant was filtered by a glass crucible filter which was dried to a
constant weight in a drying oven at 120℃±2℃ in advance. Then the precipitate
was transferred to the filter by the pouring method. The sodium tetraborate
washing solution used in the transfer of Jidan was 20mL~40mL, and then the
 precipitate was washed 5 ~7 times with the sodium tetraborate washing solution
after filtering, with the amount of about 5mL each time. Finally, wash twice with
water, about 5 mL each time. Put the precipitate together with the filter in the
drying oven at 120 ° C ±2 ° C, wait for the temperature to reach 120 ° C, dry for
15h, remove and transfer to the dryer, cool to room temperature, and weigh.
4.4 Blank test
Except without the sample, the other steps are the same as the sample solution
determination.
5. Calculation
The content of potassium, w, is expressed as %. It is calculated according to
equation (4):

(m1 -m2)×250×0.1314 (m1 -m2)×3285

w = --------------------------×100 = -------------------------- (4)
mV mV

Where:
m1: mass of potassium tetrabenylborate precipitate obtained from the test solution,
in grams (g);
m2: mass of potassium tetrabenylborate precipitate obtained from blank test, in
grams (g);
250- volume of sample solution in milliliters (mL);
0.1314- Coefficient of conversion of potassium tetraphenylborate mass to
potassium oxide mass;
m: mass of the test material in grams (g);
V- volume of sample solution partitioned, in milliliters (mL).
Conversion of mass concentration:
Liquid fertilizer potassium (K2O) content ρ(K2O), expressed as mass
concentration (g/L), calculated according to equation (5):
ρ(K2O) = 10wρ (5)
 Where:
w -- the mass fraction of potassium in the sample, expressed in percentage (%);
ρ-- density of the liquid sample in grams per milliliter (g/mL).
6. Deviation
The deviation of the test results of two parallel tests in not more than 0.3% and choose
the average value as the final result.
The mass fraction of potassium,
<10.00 10.00~20.00 >20.00
calculated as K2O, %
The test results of two parallel tests, % ≤0.20 ≤0.30 ≤0.40