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FERTILlZERS
Ammonia-Selective
in Fertilizers
Electrode Dctermillation
o Nitrogcll
n.r.
the membrane untl the partial pressure o ammonia is the same on both sides o Ihe membrane.
Ea;an and Dubois (7) noted that t1lt'
parlial pn>ssun> of ammonia and ils connmlration are relaled by PNHJ = k[NlhJ where tht>
conslant, k, varies wilh dissolved species; for Ihis
reason, Ihe ionic stren~lh of the samples and
standards must be cnnslanL
We decided to lesl the .lpplicability
of the
ammonia gas-scnsing elpclrode for lhe uell'rmination of ammoniacal anu tolal nitrogen in
fertilizers.
We compared tlw magnesium (lxide
method (MOM), which is an official AOAC
method, with an alternative melhod using the
ammonia.selpctive electrode (ASEM.l), in whch
the sample is dissnlved and ammoniacal nitrogen
is measurl'i.l dire,tiy with Ihe electrude.
We also
compared the Raney powclpr method (RPM),
which is an offical AOAC methou, with Ihe
ammonia-selt'ctivp
eleclrode nlt'thou (ASEM.2)
lhat is a variant of the RPM. ASEM-2, howpver,
consists of 2 parts: sample treatmpnt, reJuctioll.
digestion, and di5tillalion taken from the Ram>y
powder melhod; and measurement
of Ihe distilled ammoni.1 according to ASEM.I.
A majllr
simplificalion
is elimination uf the dislillation
step in dt'lermining
ammoniacal
nitrogen;
however, preliminary work show('d that it is not
possible lo measure the ammllnia cuncenlration
direclly
from Ihe solulilln
obtaincu
during
sample digestion for tolal nitrogen.
The ('Iectrode used in both ammonia-selective
plectrode
melhods was the same.
Magnesium
Oxide Method
(1\IOM) (8)
See 2.065.
Ammollia-Selective
Electrode
IASEM-l) (9)
Appdratus
dnd
Melhnd.l
Reagent.'i
tne.
BOY &: GUIJOS":
J.
acid soiution,
dilute
lo volume
wilh
Table 1.
Sample
2
3
4
valuroe with
Transfer 50
f1ask, add 20
volume with
Transfer 100
f1ask, add 10
volume wilh
;Transfer 50
flask, add 20
volume with
Oescription
Determination
Conncct ammonia el('clrode to pH meter, place
c1eetrode in working solulion 4. and warm up pH
meter. Set [uHelion switch lo Exr MV. Add 1.5
mL ION NaOH lo t:'aeh 100 ml solution.
Set
reading to 000.0 by ildjusting calibration control.
Use magnetic stirrer at conslant rate throughoul
procedure.
Addition o NaOH lo evolve NHJ is
exothermic.
A change in temperature wiH cause
eeetrode response lo shift and change slope.
Samples and standards should be at same le mperature, [or convenience, room temperature.
A
1C difference in temperature will cause ca 2%
measuremcnt error (9). Place electrode in each
solution and read mV o[ working solutions .1nd
unknown sample solutions.
Plot mV rcadings
(linear axis) againsl concentration
(Iog ilxis) on
standard 3- or 4-cycle semilogarithmic
paper.
Determine ammoniacal nitrogen conlent o[ unknown samplE's [rom standard curve.
AftE'r 2 readings, recalbratc eleclrnde by using
working solution 4.
samp1es studled
8
9
10
11
12
Description
30.0.0. Magruder 7905 B liquid
check sample
5.10.15. Magruder 7908 solid
check sample
11.54.0. Magruder 8003 B MAP
check sample
18.46.0, Fertilizer grade
diammonium phosphate
21-0.0, Ammonium sullate.
reagent grade
35-0.0, Ammonium nitrate.
reagent grade
Same as Silrnple 1
10.34.0. Magruder 7907 B 1iquid
check sample
9.27-6. Milgruder 7807
suspension check silmple
12-1 S-lO. Magruder 7709
suspension check sample
19.19-19. Magruder 7712 solid
check sample
3-9.9. Magruder 7607 solid
check Silmple
Raney Powder
01 fertlllzer
Appro;<;
ammoniaCill
N conten!,
1097
Method
8.0
3.0
11,0
18.0
21.0
17,0
(lH"M) (8)
SE'e 2.063-2.064.
Ammonia-Scleclivc
Eeclrade
(ASEM-2)
Mclhod~2
(8, 9)
Delerrnination
For sample pretrcatmenl, reduchon. di~estion.
and dislillation, see 2.064. For measuring ammonia in distillate, see l1cfermilUltiOIl
in ASEM.
L
Results
and Discussion
Ammonacal Nitrogen
Six samples (1-6, Tilblc 1) werc analyzed in 6
replicates for ammoniacal nitrogen by MOM and
ASEM-l, respeclivcly.
l-iowcver, Magruder
check sample 7905 U was not analyzed by MOM
bccause il contains urea anJ this method is nol
applicable.
Sample 7905 B was anillyzed by 18 participant
laboratorics in Ihe MagrudE'r check samplE' program, SamplE' 7908 by 5 laboratories. and SamplE'
8003 by only olle laboratory (10). The diammonium phosphalE' sample was analyzed by 8
laboratories in a priva te inlerlaboratory proj2;ram.
1098
Table 2.
/. ASSOC.
OFF.
ANAL.
CIiEM.
(VOL.
64,
NO.
S,
1981)
Comparison 01 results by olficial magneslum oxide and ammonla-5elective electrode methods on 6 samples
01 !ertilizers
Ammoniacal N. %
Average
Std dev,
Coelf. 01var,. %
Sample
Magruder
results
MOM
ASEM-l
MOM
ASEM.1
MOM
ASEM-I
1
2"
3"
4"
5b.c
6~.d
7.718 :r 0.3648
2.7040:t 0.0430
11.035 :t 0.0786
18.24
:1:0.17
21.20(theor.)
17.50(theor.)
2.717
11.088
18,267
21.138
17.527
7.547
2.593
11.213
18.058
21.063
17.232
0.0288
0,0821
00907
0.0417
0.0698
0.1084
0.0557
0.0393
0.0454
0./224
0.0527
1.060
0.740
0.497
0.197
0.398
1.436
2.148
0.350
0.251
0.566
0.306
Total Nitragen
Six samples (7-12, Table 1) were .:malyzcd in
6 replica tes for lotal nitrogen by RPM and
ASEM-2. Samples 7905 B, 7907 B, 7807, 7709,
7717, and 7607 were analyzed by 5, 5, 6, 7, 5, and
Table 3.
Comparison 01 results by official Raney powder and ammonia selectiye methods on 6 samples 01 fertilizers
Nitrogen, %
Ayerage
Sample
7"
8"
9
lOa.b
11
12
Std dev.
Magruder
results
RPM
ASEM.2
RPM
29.21O:r 0.1379
9.758:r 0.0944
9.35 :l:0.07
11.98 :1:0.09
1928 :1:0.29
3.1929:1:0.2615
29.175
9.853
9.367
12.000
19.195
3.175
29.427
9.947
9.530
12.098
19.275
3.277
01465
0.1934
0.1106
0.0335
0.1349
0.1203
ASEM.2
0,0962
0.1473
0.0844
0.0776
O.llOO
0.0922
Coelf. 01var .. %
RPM
ASEM.2
0.502
1,963
1.181
0.279
0.703
3.789
0.327
1.481
0.886
0,641
0.571
2.814
BOY & GUIJOSA:
J-
ASSOC.
OH.
fOf
confine determination
of ammoniacal nitrogen.
It simplifies Ihe normal procedure because Ihe
distillation step is omitted. In the determinatian
oC total nitrogen with the Raney powder method,
the final titration can be substituted by an electrode measurement,
hut with no improvement
oC results.
REFERENCES
ANAL.
CHEM.
(VOL.
(,4, NO.
S, 1981)
1099
TX
R. F., & Booth, I{. L. (1973) I1l'iro/l. Sci.
7,523-526
Cilbert, T. R.,& Clay, A,
(1973) Aual. Clre1/!. 45,
1757-1759
Renfro, L.J., & Patel, Y.(I974) f. AI'I,I. PII.IISilll.37,
756-757
Barbera, A., & Cant'pa, D. (1977) 1- AS."Ilf. Off. Al/al.
OCIII. (,0,708-709
Woodis, T. c., Jr, & Cummings, J. M., Jr (1973)'.
Assoc. 0lf. Allal. Chem. 56,373-374
Eagan, M. L., & Dubois, L. (1974) Al1al. CJjm. Aria
70,157-167
0l/icial Metlwds o/ Al1/1I.II';S (1980) 13th Ed., AOAC,
Arlington, VA, secs 2.065, 2.063-2.064
'Ilstmclioll
Manual Irlr Ammon;a Elec/rode i\ltJdl'1
95-10 (1975) Orion Researeh, Ine., Cambrd~e,
(2) Thomas,
TccJl/Illl.
(3)
(4)
(5)
(6)
(7)
(8)
(9)
"'1.
MA
(10) Statistical Evalualion on 7607, 7709, 7712, 7807,
7905 n, 7907 n, 7908, and 8003 M<lgrudE'r Chcck
samples (1976-1980) Magruder
Cheek Sampl('
Series, Atlanla, GA
(11) Dixon, W. J. (1953) B)/l1l'lrks 9,74-89
J1nalytical
Chenusts,
COROMINAS
551
Sludy
Table 1 shows the 8 samplcs used Eor comparative evaluation. Thrcc samples were comrncrcial fertilizers of unknown
sodium con-
centration, 2 samples were Magruder NPK fertilizer check samples, 2 were synthetic NPK
samples, and one was 7804, Magrudcr muria te
check sample, mentioned earHee. Samples were
selected to test the applicability of the peoccdures to different types oE products and levels
of sodium content. Ten replica te determinaIions were performed on each sample for each
method.
METHODS
1. F1ame Emission Spectrophotomelric
Method 1 (FES Methud-l)
See 2.147-2.150 (4). Readings were made using
Model Mark 11 flame photometer (available fraIn
Evans Eledroselenium
Ltd), wilh air-propane
flame.
n.
and Reagents
(a) Atomic
absorptioJl
spectropllOfometer.Model AA6 (Varian Techlron Ply Ud), or equivalent.
(b) SodiulIl so{utiolls.-(l)
Stock SOIIl/OlI.1000 IIg Na/mL Disso]ve 2.5421 g rure NaCI in
ca 3-5 rnl HCI (1 + 1). Di]ule lo 1 L (2) Working
standard solutioIlS.-O, 20, 40, 100. and 200 M~
Na/ml. To 250 ml volumelric flasks, add O. 5.
10, 25, and 50 ml Na stock solulion. Adjusl each
standard to ca o.lN in HCI (aboul 0.8 ml HCII
100 ml) and dilule lo 250 mL.
Preparation
of Sample Solution
Rece;ved
000"-'7'6/80/6303--0"1-03$01
,00
~ A o(iolion of Offieiol Anolylicol Chemi,h,
In(.
Dl'cl'mber
U. 1979.
552
COROt.UNAS
Table l.
Description
Sample
A
B
e
O
E
ET AL.,
01 lertili;ter
J.
samples
Approx.
sodium
contenl,
%N.
Oescriplion
rnurlate, 0.0.60, Magruder 1804cheCk
s8mple
DAP, 18.46.0,fertilizer grade dium.
monium phosphate
su perphosphate, 0.20-0,lertillzer grade
normal superphosphale
19'19-19,Magruder Iquid check sample
12.}5-10,Magruder sol id check sample
studled
1.0
0.1
Determination
o
Iectrode
Method
and Reagents
of Solulion
and Discussion
COROMINA5
orF.
J,
553
1980)
Table 2. Comparative results lor the det rmlnatlon 01 !!Iodlum(% Na) In 8 samples 01 ferUlizers
Method
Slatislic
11
Melhod
111
IV
11
Sample A, Muriate
Average
Std dev.
Coer!.of
var., %
1.538
0.030
1.447
0.010
1. 449"
0.013
1. 809
0.014
0.080
0.007
0.09l"
0.004
0.098
0.006
0.111
0.009
1.951
0.691
0.897
0.774
8.750
4.301
6.122
8.109
Sample D. 19.19.9
0.130
0.008
0.159
0.008
0.232"
0.004
o.on
0.211
0.602"
0.007
0.605
0.009
0.512
0.008
0.714
0.027
6.1S4
5.0]1
1. 724
6.161
1.167
1. 488
1.56]
].782
Sarnple E. 1l.15.1O
Average
Std dev.
Coell.ol
var . %
Sample F. Urea
0.200'
0.008
0.230"
0.007
0.173
0.004
0.260
0.005
4.000
3.043
2.]12
1. 9lJ
NO'
0.00246
0.00040
16.260
IV
111
0.00103
0.00013
12.621
0.0079
0.0010
12.658
0.861~
0.058
1.312
0.116
1.108
0.008
0.790
0.027
0.133
0.005
0.117
0.003
0.119
0.000
0.084
0.004
6.736
8.841
0.712
3.418
3.759
2.564
0.000
4.76l
In this sel, one value was rejeeted at 95% significanee leve!. Dixon test (9).
~ Not deteeted.
<1
Acknowledgmenl
The authors thank P. Rojas for his help in
the realization of the laboratory work.
REFERENCES
Off. Anal.
Off. Arla/.