1096

DOY & GUIJOSA,

J. ASSOC. OFF. ANAL. CIIEM,

(VOL. 64, NO. 5, J9RI)

FERTILlZERS
Ammonia-Selective
in Fertilizers

Electrode Dctermillation

o Nitrogcll

VICTOR M. HOY and MANUEL GUljOSA

Fertilzl1Iltes Mexicallos, S.A., SlIbgerencia de IllvesfigllcilI, Chiapas 184, Mxico 7,
The official AOAC nldgnesium ollide method
(MOM), 2.065,fOfdeterminin; ammnnill:ai nitrogen
in fertilizen; not containing ure,l was compared with
.In alternative anllllonia-se1ective electrode rnethod
(A5EM.1). likt-wise, the official AOAC Raney
pnwJer nlelhod (l{PMI, 2.063.2.064, for Jelt"fmining
, total nitrogen in fertilizers, except nitric phosphates
cOlltaining nOllsulfate S, WolS
compareJ with an am.
mnnia-se1eclive electrode method (A5EM-2). Each
comparison includeJ 6 s<lmples. For ammuniacal
nitrogen determinatiOIl, MO~1 and ASEM.] showeJ
equivalent precision, although si;nificant statistical
differences were obtained in av("rage values for tht>
moljorily of sdlnples. For 10la1nitrogen Jett"tmilldtion, RPM and ASEM.2 show("J equivalent precision,
although signific.lnt slatislical differences were obtaineJ in 3 samples. The AOAC official methods
showeJ beller olccuracyIhan ASEM.l ,lnJ ASEM-2.
l1ow('ver, Ihe accllracy and precision of ASEM-l for
ammoniacal nilrogen is suililble for routine work.
The avalability
of the ammonia gas-sensing
e\eclrode offers Ihe possibility of using a rapid
and inexpensive technique lo simplify nitrogen
delerminaton
in fertilizers and olher producls.
The instrument has been used for nitrogen determinalion by Ihe known addition technique in
fertilizers and protein in feeds (1), and ammoniacal nitrogen in water and wasles (2) and
sea water (3). Sorne studies o urea analysis have
also been made using Ihis electrode (4, S), with
good results. Woodis and Cummings (6) studied
lhe cletermination
of ammoniacal nitcogen in
fertilizers containing
urea, using this type of
electrode; Iheir results were in good agreement
with those of the reduced pressure distillation
method.
The Orion ammonia electrode conlains a hydrophobic
gas.permeable
membrane
which
separates the test solution fram Ihe electrode
internal solution.
This membrane prevenls a
false response lo dissolved ions. Howevef, high
levels of ions can affect Ihe solubility of ammo.
nia. Thomas and Booth (2) indicaled Ihat dis.
solved ammonia in lest soluton diffuscs Ihrough
rn"M"nted atlh 94th Annual Met'tng of the AOAC. Oct,
20-23.1980, al Washington. DC.
Received August27,

1980. Accepled February 26, 1981.

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

(a) Amfllollia dectrode.-Orion Moul'l 95.10

(Orion Research nc., 380 Putnam Ave, Cambridge, MA 02139).
(b) pH ml'!er.-Orilln
Model 70{, or equivalent.

0004-5756/81 /6405.\ 096.04 $1 00

@Associat;ono'OlfieiaIAnalytieaIChemists.

tne.


BOY &: GUIJOS":

J.

ASSOC. OrFo ANAL

(e) Tar/arie acid soll1lioll.-lO% aqueous solution.

(d) Sodilllll 1l.lIdroxidc solulioll. -ION.
(e) Ammolliacalllitrogcll
so/uliolls.-Slock
so/ulio/l.-1400 ~g N/mL. Dissolve 5.35 g Teagent

grade NH4Cl in water in 1 L volumetric flask and

dilute lo valume with water, Workillg 50/111;0115.-( J) 700.ug N rnL. Transfer 100 mL stock
solution lo 200 ml volurnclric f1ask, add 20 ml
tartaric

acid soiution,

dilute

lo volume

wilh

Table 1.

Sample

2
3
4

rnL solution 1 lo 250 rnl volumetric flask. add 20

mL tartarie acid solution. dilute lo volume with

water, and mix. (3) 70 .ug N mL. Transfer 100

rnl solulion 210 200 ml volumetric flask, add 10

valuroe with
Transfer 50
f1ask, add 20
volume with
Transfer 100
f1ask, add 10
volume wilh
;Transfer 50
flask, add 20
volume with

Oescription

Place sample containing 10-50 mg ammoniacal

N in 250 mL volumetric f1ask, and add 25 ml
tartaric acid solution <Jnd 100 mL water.
let
stand 15 min, swirling occasionally.
Dilute to
volume with water, and mix.

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

Preparation of Sample Solution

01 fertlllzer

Appro;<;
ammoniaCill
N conten!,

water, and mix. (2) 140.ug N {mL. Transfer 50

rnL lart<'lric acid solution, dilute lo

water, and mix. (4) 14 .tg N/mL.
ml solution 3 to 250 ml volumetric
ml lartadc acid snlution, dilute lo
water, and mix. (5) 7.0 .tg N/mL.
ml solution 4 to 200 mL volumetric
ml tartaric acid solution, dilule lo
water. and mix. (6) 1.4 .tg N/mL.
ml solution 5 to 250 mL volumelric
mL lartaric acid solution. dilute to
waler, and mix.

1097

CHEM. (VOL. 1>4, NO. 5, 19f1l)

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)

Apparafus and Ueagents

See 2.063 and ASEM-l.

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.

HOY &: GUIJOSA:

/. 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

~ Significant dillerences in averages al 95% leyel, t-test.

1> Ammonium sulfate. reagent grade.
e Signilicant differences in stilndard deviation at 95% level, F-test.
d Ammonium nitrate. reagent grade.

Thc ammonium sulfate and ammonium nitrate

samples were reagent grade.
Mean per cenl nitrogen, standard deviations,
and relative standard deviations (CV,%) for each
of the samples by both methods are given in
Table 2. No value was rejccted at the 95%significance level by the Dixon test (11), When
standard deviations were compared by means of
the F-test, differences were statistical1y significant only for the ammonium sulfate samplc,
which indicatcs equivalent prccision for both
mcthods:although the l-test showed significant
statistical differences in the averages for 4 of the
5 samples studied.
Therefore, MOM and
ASEM-l gave comparable prccision, but average
values for MOM are in bt'tter agreement with
refcrence values than are averages for ASEM1.

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.

7 participant laboratories, respectively, in tlw

Magruder check sample program (lO).
In a preliminar)' cxperiment with ASEM-2,
nitrogen was measured wilh the ammonia-selective electrode directly ater digestion; howw
ever, values were very high. These high values
mal' be due to the increascd ionic strength of the
solution caused by solids forml'd during the addition of NaOH to evolve ammollia. Such results an' in accordanc{' with observations by
other authors (2, 7) who recommended that
samples ano standards have the same ionic
strength. Further studies are necessary to consider this eHecL
Mean per cent nitrogen standard deviations,
and coefficienls of variation for t'ach ()f the
S<lmplesby both mcthods are given in Table 3.
When standard deviations were compared by
means of the F-tesl, differences were statistically
significant only for Sample 7709, which indicates
an equivalent precisiun of bolh nwthods, although the t-test showed significant statistical
differences in the averages for 3 of the 6 samples
studied (50%of the total formed pairs).

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

~ Signllicant dilferences in averages at 95% level. !-lest,

J:> Significant diflerences in standard deyiations at 95% level. F.test.

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.

In general. the average valucs fOf arnmoniacal

and total nitrogen by MOM and RPM are in
better agreement with the referenee values than
are lhe average valucs ohtained by ASEM-l and
ASEM.2. This means that the ac(uraey of the
magnesium oxide method and RalH'Y powder
rnethod are better Ihan those obtained by am-

monia-selective ec(trode tcchniques. 00 the

other hand, Ihe average vaJues ohtained
by
ASEM.l and ASEM-2 are higher than those oblained by MOM Uf RPM.
The accuracy and precision of Ihe ammonia-

selective electrode technique is suitable

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

(1) Hoove-r, W. L., Colvin, B. M., Me!ton, J. R., Hanks,

A. R., & Howard, P. A. (1977) De-terminalion of

ANAL.

CHEM.

(VOL.

(,4, NO.

S, 1981)

1099

nilrogen in fertilizers and protein in feeds by the

Orion ammonia ('('ctrode, Bull. Prpl. AXri . A/lul.
Srrvirrs, TeXilSA&M University, ColI('g(' Slation,

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

Heprintcd from the J(!urnal (lf Ihe J1ss(Jciatioll (Jf Official

Vol. 64, ScptemIJcr 1981

J1nalytical

Chenusts,

COROMINAS

551

ET Al..: l. ASSOC. OFF. ANAL. CHEM. (VOl. 63, NO. 3. 1980)

Preliminary ComparisoH of Methods for Determining

Sodium in Fertilizers
LUIS F. COROMINAS,

VICTOR M. BOY, and MANUEL GUIJOSA

i=erfilizllntes Mexicanos, S.A., Resellrcll Division, Zacatecas 80, Mxico 7, D.1=.

The AOAC offidal hrst action method 2.1472.150 for the f1ame emission speclrophotometrk
(fES) determinalion of sodium in ferlilizers was
compared wHh the atomic absorption spectrophotometric (AAS) method and Ihe sodium selective electrodc (SSE) method. Two synthetic NPK
samples, 3 commercial samples (urea, DAP, and
superphosphate), 2 Magruder NPK check samples,
and one Magruder muria te check sample were
used for the study. Slatistically significant differences were obtained in both averages and standard
deviations for all samples. In general, the precision for all methods was acceptable; the AAS
method seems to be the more accurale the AOAC
method needs lo be revised; and the SS[ melhod
has the tendency lo give higher values. Addilional
experimental work is necessary to define which
method is the most convenient.
Previous experimental
work (1-3) on the
detcrmination
oE sodium in Eertilizers resulted
in the adoption oE the AOAC officia.l Hrst action method 2.147-2.150
(4), which is based
on a fl.1mc cmission spectrophotomelric
peocedure (FES). It seems thal this method is not
used in many laboratorics.
The Magruder report for Samplc 7804 (5) showcd Ihat 23 Ia.boratories repoded
valucs Eor sodium and oE
these. only 5 used the FES method .1nd 17 used
an atomic absorption spectrophotometric
procedure (AAS). The availability
oE a sodium
selective electroue (SSE) suggested the possibility oE applying this tcchnique to the determination
of sodium
in fertilizers,
thus
greatly simplifying the analysis.
'"Ve dccided to perEorm a preliminary study
comparing the official AOAC procedure (FES
method) with the 2 aIternative methods. The
FES method was tcsted using 2 different types
oE equipment and flamesj the AAS rnethod
was adapted frorn a procedure for phosphate
rock (6)j and the SSE mcthod was established
Eollowing the recommendations
from the elcctrode 5upplicrs (7, 8).
Comparative

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.

Flame Emission Spectrophotometric

Method 2 (FES Method-2)

See 2.147-2.150 (4). Readings were made using

Model AA6 atomic absorplion spectropholometer
(available from Vrian Techlron Ply Ud) in emissioo mode. wilh air-acetylene flameo
111. Atomic Absorption
Spectropholometric
Method (AAS Method) (5)
Apparatus

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

Weigh 1.00 g sample into 250 ml beaker. add

15 ml HCI (1
1) and digesl 15 min on hol plale.
Filter Ihrough fas! paper inlo 250 ml volumelric
f1ask. washing paper and residue Ihoroughly with
waler. Measure absorption of soIution directly or
dilule with o.IN HCI to oblain soIulion within
range of inslrumenl.

Rece;ved

AUlI:u,1 30. 1979. Accet>led

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.

ASSOC. OFF. ANAl.

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

urea, 46.0-0, ferlilizer grade urea

20.20.20, synlhetic sample, prepd with

diammoniurn phosphate, potassium
chloride, and sodium chloride.
reagent grades
same as Sample G

studled

1.0

0.1

Determination
o

5et wavelength al 5890A. Adjust burner hcad

900 to bcam oc anolher position if preferred lo
reduce sensitivity, using air~acetylene flameo Asprate standards and unknown samples. PJol curve
from standard values and determine Na content of
unknown samples from plot of absorplion against
.g/mL
IV. Sodium Selective

Iectrode

Method

(SSE Me.hod) (7, 8)

Apparatus

and Reagents

See 2.091(a)-(b) and

(e) pH meter.-Model
701 Digital (available
from Orion Research,
lnc., Cambridge,
MA
02139), or equivalent.
(d) Eleetrodes.-Sodium ion seleetive glass electrode and reference eleclrode Models 39278 and
39402 (Bcckman Instrumcnts, Inc., Fullerton, CA
92634), or equivalent.
(e) Sodium solutjOllS.-Stock SOllaioll,-IOOO flg
Na/roL. Dissolve 2,5421 g pure NaCl in 800 ml
water. Adjust to pH 10 wilh concentrated ammonium hydroxide and dilute lo 1 L. Workg
solutiolls.-(l)
500 .g Na/mL. Transfer 100 ml
stock solution to 250 ml beaker, add ca 50 ml
water, and adjust to pH 10 with coneentrated
NHOH. Transfer to 200 ml volumetric flask,
dilute lo volume with waler, and mix. (2) 100 .g
Na/mL. Transfer 50 ml 50lution 1 to 250 rol
beaker, add ca 150 ml water, and adjust to pH 10
with concen!rated NH40H. Transfer lo 250 rol
volumelric flask, dilute to volume with water, and
mix. (3) 50 .gNa/roL. Transfer 25 ml Solution 1
to 250 ml beaker, add ca 175 ml water, and ad.
This "'po.1 01 the As~odale Referce wa, p.e,enled al lhe
9Jrd Annual Meeting of lhe AOAC, Oct. 1.5--1&,1979, ilt
W,)shin:lon, OC.

CHEM. (VOL. 63, NO. J, 19~O)

just to pH 10 with concenlraled NH,OH. Transfer

to 250 ml volumelric f1ask, dilule to volume wilh
water, and mix. (4) 10 .gNa/roL. Transfer 25 rol
Solution 2 to 250 rol beaker, add ea 175 rol water,
and adjus! lo pH 10 with concentrated NH,OH.
Transfcr to 250 ml volumetric flask, dilule lo volume with water, and mix. (5) 5 .gNa/mL. Transfer 25 ml Solution 3 lo 250 ml beaker, add ca
175 ml waler, and adjust to pH 10 with concen!rated NH10H. Transfer to 250 ml volumetric
f1ask, dilute to volume wilh waler, and mix. (6) 1
.gNa/ml. Transfer 25 ml Solution 4 to 250 ml
beakcr, add ca 175 ml water, and adjusl to pH JO
wilh concentratcd NH,OH. Transfer to 250 ml
volumetric f1ask, dilute to volume wilh water, and
mix.
Preparation

of Solulion

Prepare solution as in 2.093(a), using sample

containing ca 25 mg Na, in 250 ml beaker. After
boiling adjust lo pH 10 wilh NH,OH. Transf('r lo
250 ml volumetric f1ask, dilute to volume wilh
waler, mix, ami pass through dry filter.
Determination
Conlled Na and reference elcctrodes lo pH
meter, place electrodes in low concentration Na
solution, and warm IIp pH meter. Transfer C.1 100
ml stock, working, and unknown sample solulions
into sep.1fale 250 ml I;.eakers. Place electrodes in
each solution and while stirring wilh magnetic
stirrer al constan! rate, read mV of the stock
working and unknown sample solutions. Rime
and blol c1ectrodes between solutions. Plot Ihe mV
rcadings (linear axis) against concentralion (Iog
axis) on standard 3- or 4~cycle semilo;arithmic
paper. Determine Na content of unknown samples
from slandard curve.
Results

and Discussion

The averages DE the 10 determinations

madI"
on ea eh s.lrnple with eaeh method, and the corrcsponding standard deviations and eoefficients
oE variation, are shown in T able 2. In general,
the standard
deviations
for the 4 methods
showed
precisiom
that are aeeeptahle,
alIhough the F-Iest showed significanl s!atisticai
diffcrenecs in 50% oE thc total pairs that can
be formed. Comparing
the averages by mean"
of the t-test showed signiricant statistical differences in 70% of the total pairs.
Differences
are evident between the averages for the 2 versions of Ihe FES method, anJ
this can only be attrihutcd to thc use of differcnt equipment
and different
Aame Ch.1fileteristics thus, the AOAC official method need
to be revised. In the Magruder
report for
Sarnple 7804 (Sample A), the avcrage for tite

f.T AL.: J. AS50C.

COROMINA5

orF.

ANAL. CHEM. (VOL. 63, NO.

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

Sample G. lO-lO.lO. Synlhetle

Average
Std dev.
Coefl.ol
var . %

IV

Sarnple B, Diamrnonium Phosphate

Sample C, Normal Superphosphate

Average
Std dev.
Coeff.ol
var.. %

111

0.00103
0.00013
12.621

0.0079
0.0010
12.658

Sample H. lO.20.20. Synthetie

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

FES method was 1.095% Na (5 lahoratories),

and 1.439% Na (17 Jaboratories) for the AAS
method, which are similar to the 1.538% Na
value for FES Method-l, 1.447% Na for FES
Method-2, and 1.449% Na for the AAS
method. The agreement between the values for
the AAS and FES Method-2 is exceIlent.
The theoretical values for Samples G and H
(synthetic samples) were 1.031 and 0.126%
Na, which agree with the averages for the
AAS method, 1.108 and 0.119%. High standard deviations were obtained foc the other
mcthods in Sample G. Sample F has the most
variable results, showing that the evaluated
procedures are not adequate for very low leveIs
of sodium contento
The SSE method has the tendency to give
the highest results. Initially, the sample for
this method was treated with Hel (1+1), but
the results were erra tic, so the same sample
treatment (oxalate extraction) specified in the
official AOAC procedure was used. It secms
that the AAS method has a better performance than the FES methods or the SSE method,
but the results of the study do not permit the
selection of the most convenient method.
It is recommended that study continue.

Acknowledgmenl
The authors thank P. Rojas for his help in
the realization of the laboratory work.
REFERENCES

(1) Corominas, L. F. (1972) ]. Assoc.

Off. Anal.

C}em. 55, 986-988

(2) Corominas, L. F. (1973) ]. Assoc. Off. Arla/.

C}ern. 56, 859-861

(3) Corominas, L. F. (1974) ,. Assoc.

Off. Arla/.

CIJelll. 57, 1402

(4) OfJicial MetIJOlls of Analysis (1980) 13th Ed.,

AOAC, Arlington, VA, secs 2.147-2.150
(5) Statisticai Evaluation on 7804 Magruder Check
Sample (1978) Magruder Check Sample Series,
AtIanta, GA
(6) MetllOds Used and Adopted by the Associatiol! of Florida Phospll1Tte CIJemisls (1970) 5th
Ed., AFPe, 8artow, FL, Sec IX, Method 13
(7) Se/ecHon Sodium /ectrodes, Beckman lm;tructiol1s 015-081155.D (1975) Beckman Instrumen!s, Inc., Fuilerton, CA
(8) l'lstrucliotl
Manual
for Sodium /ecfrodes
Models 94-11 arld 96-11 (1977) Orion Research, Inc., Cambridge, MA
(9) Dixon, W. ]. (1953) Biometrics 9, 74-89
Th{' recommend~Uon 01 the Associ~te Refer{'e w~s ~l'proved by the Rderee an<.l Subcommittee A a.nd was ~ccepted by the Associa.Hon. See ,. Auoc. Off. Aun/. Che",(1980) 63, 297.