1962 DAtILGREN:Simplification of the quinoliniumphosphomolybdate method 243

References
1 B d K ~ , F. B., T. W. Nv.WTO_W and ~ . K ~ - ~ : g. physic. Chem. 64, 109
(1960). -- 2 Bnc~cBxwf, N., and S. ~ . Em~O~DS: AnMyt. Chemistry 12, 155 (1940);
cf. Z. anMyt. Chem. 124, 120 (1942). -- a BImcBkv~, N., and G. I-L W.~Lm~:
J. Amer. chem. Soc. 60, 64 (1938). -- ~ EwINo, D. T., and M. WrLSO~: J. Amer.
chem. Soc. 81, 2105 (1931). -- 5 ~tm~A~, N. H., and G. H. WAr,Dye: J. Amer.
chem. Soc. 60, 64 (1938). -- 6 GRv]3ITsc~,H., K. Hta~vo~sE~ and G. SemNDL]~:
Z. analyt. Chem. 178, 414 (1960). -- ~ M~soN, W. B., J. S. P]~KOL~t and N. It.
IFu~AN: Report A, 1061, Nov. 17 (1944). -- s ~MIc~VLIS,L., and S. G~A~cK:
J. Amer. chem. Soc. 68, 1636 (1941). -- 9 PEKOLA,J. S., and N. H. FUR3~AN:
Report A., 1041, See. 2F, gun. 30, (1940). - - ~0 RAO, G. GoP~x, and M. SV~YA~A-
~xYA~r Z. analyt. Chem. 169, 161 (1959). -- n Rxo, V. P., and G. G o r ~ A R.to:
Talanta (London) 1, 355 (1958); cf. Z. analyt. Chem. 171, 39 (1959/60). -- ~ RAo,
V. P., ]3. V. S. R. M y l a r and G. Go~A~x RAo : Z. analyt. Chem. 150, 401 (1956). - -
~a SILL, C.W., and H. E. P]~TE~SO~: Analy% Chemistry 24, 1175 (1952); cf. Z.
analyt. Chem. 143, 306 (1954). -- ~a WAnDE~r G. H., L. P. HA~nTT and S. Nf.
EDmOnDS: J. Amer. chem. Soc. 56, 350 (1934). -- x~ WILL~a~D,H. It., and P.
~'. YovNr J. Amer. chem. Soc. 55, 3260 (1933).
Prof. Dr. G. GO~AL~R~.O, Head of the Department of Chemistry,
Andhra University, Waltair (India)

Research and Development Department, AB F6rcnade Superfosfatfabriker,

Landskrona, Sweden

Simplification
of the Quinolinium Phosphomolybdate Method
Using Acetone-bearing Reagent Solution
With Reference to the Analysis of Fertilizers
By
SVEN-~ERIC DAHLGREN
With 4 Figures in the Text
(Received February 5, 1962)

Owing to its m a n y benefits, the qttinolinium p h o s p h o m o l y b d a t e

method for d e t e r m i n a t i o n of phosphorus has created great interest. I t is
r a t h e r simple to carry out a n d gives a precipitate of a defined chemical
composition i n c o n t r a d i c t i o n to t h e old p h o s p h o m o l y b d a t e method.
WrLso~r developed a volumetric modification, which r e c e n t l y has
been accepted as official for fertilizers a n d feeding stuffs i n the U n i t e d
lf~ingdom 12. A gravimetrie modification b y PEI~RIN 1~ gives a v e r y
great accuracy. The q u i n o l i n i u m p h o s p h o m o l y b d a t e m e t h o d has been
extensively used for the analysis of iron ore a n d steel 1, ~, 4-s. Of special
 244 SvEN-ERIc D~LGREX Bd. 189

interest is the introduction of acetone into the reagent solution 4 accom-

panied b y a considerable simplification of the analytical technique.
Z]~CH~Eg and REI)PESTAJY116 applied this modification to the analysis of
condensed phosphates.
The quinolinium phosphomolybdate method has as yet one serious
drawback in the analysis of fertilizers. I t is susceptible to interference b y
ammonium above a rather narrow limit. This is no problem in the United
Kingdom, where fertilizers are sold on basis of their water solubility. In
other countries, where the commercial base is extraction b y neutral or
alkaline ammonium citrate solution the method has been abandoned for
this purpose. The object of this investigation was to eliminate the ammo-
nium interference and make the quinolinium phosphomolybdate method
generally adaptable for fertilizer applications.
Preliminary Studies
I n his procedure WrLso~la, 15 used two reagent solutions, one con-
raining sodium, molybdate, citric acid and hydrochloric acid and the
other one quinolinium and hydrochloric acid. FERNLUND and ZECHNER4
used no citric acid and introduced acetone. I n the presence of acetone, an
oxidizing medium is necessary, therefore a mixture of nitric acid and
hydrochloric acid was used. The ingredients were combined in a single
reagent solution. I n the analysis of fertilizers citric acid is necessary to
eliminate the interference of silica. I t was therefore logical to complete
the latter procedure with citric acid. Preliminary trials showed t h a t in the
presence of citric acid, the amount of mineral acid as well as quinolinium
have to be reduced to obtain a complete precipitation and a good physical
condition of the precipitate. After these changes it was stated that a con-
siderable amount of P ~ T ~ , ~ A ~ solution, (ammonia alkaline ammonium
citrate solution) could be introduced without influence on the analytical
result. The above mentioned drawback concerning the quinolinium
phosphomolybdate method thus had been eliminated.
I t is considered t h a t the ammonia interference is eliminated by a
reaction between ammonia and acetone similar to the reaction between
hydroxylamine and acetone or ammonia and aldehydes. ALFET,T1 found
t h a t nitric acid was to be preferred to hydrochloric acid. The same findings
were established in the present study and hydrochloric acid was therefore
omitted in the later work. F r o m this starting point a systematic study
was undertaken of different variables and tolerance limits of some inter-
fering substances.
Procedure
Solutions. Quimociac Reagent Solution. Dissolve 70 g of NaeMoO~. 2I-I20 in
150 ml of water. In 150 ml of water dissolve 60 g of citric acid monohydrate and
add 235 ml of cone. nitric acid, sp.g. 1.40. Add the molybdate solution to the citric
acid--nitric acid solution under agitation.
1962 Simplification of the quinolinium phosphomolybdate method 245

Add to i00 ml of water 35 ml of cone. nitric acid sp.g. 1.40 and then 5 ml
of quinolinium. Add this solution to the molybdate-- citric acid--nitric acid solution
and mix well. Preferably let stand over night and filter through a wrinkled filter
~unktell nr 20 or 920 or equivalent. Then add 280 ml of acetone and dilute with
water to 1000 ml.
Notes. Technical grades of all above mentioned ingredients arc acceptable.
85 per cent molybdic acid, dissolved in sodium hydroxide, is not to be used, as it
contains considerable, not specified, amounts of ammonium molybdate.
Depending on the quality of the ingredients, sometimes the precipitation of the
impurities is complete within a few minutes, sometimes the precipitation is very
slow and the solution turbid. It is therefore necessary to give the preoipltation
sufficiently long time to be complete before filtration.
Filtration must be done before addition of the acetone, because the acetone
concentration in the quimociae solution is high enough to dissolve the precipitated
impurities.
After addition of the acetone the solution sometimes is a little turbid caused
by very minute gas bubbles. The solution becomes clear after a few hours.
Indicator. Mix 2 parts by volume of 0.i per cent phenolphthalein solution with
3 parts of 0.1 p~r cent thymol blue solution. Both indicators are dissolved in ethanol.
Per 100 mg of thymol blue add 2.2 ml 0.1 normal sodium hydroxide.
Sodium Hydroxide and ttydroeh~oric Acid both 0.5 normal.
Precipitation. An aliquote, containing about 50 mg but not more than 70 mg
P205, of the sample, is brought into a beaker or an E)/[-flask. Dilute with water to
about 100 ml and add 100 ml of quimociac solution. Immediately cover with
a watch glass and warm to simmering, about 75 ~C, and keep this temperature for
about 30 see. Work in a fume hood. Open flame must not be used. When heating
on a hot-plate, place the beaker on a steel net to avoid spattering. Do not shake or
agitate when adding reagent solution and while heating, as this causes formation
of lumps, which are difficult to dissolve in sodium hydroxide. Let cool until the
beaker can be handled by a naked hand, and shake or swirl 3 - - 4 times during
cooling. Note. Precipitate forms first upon heating.
Volumetric Modification. A glazed porcelain filter plate of the Witt type, 20 to
25 mm in diameter, with coned edge, is placed into a smooth funnel connected to
vacuum. Place a filter paper 1Vfunktell 0 0 H or equivalent with 4 to 5 mm larger
diameter than the filter plate on this and moisten. Add 25 ml of cellulose powder
suspension, containing 3 g of powder per liter, and suck dry.
Wash the precipitate 6 times by decantation using about 30 ml of water each
time. Pour the decantate into the funnel. Transfer remaining precipitate by means
of a water jet. Wash 4 times with water and suck dry each time.
Place the funnel over the beaker used for the precipitation. With a glass rod
suspend the precipitate in a few ml of water and place the filter plate in inclined
position. Wash the precipitate into the beaker and transfer the filter paper also.
Suspend the precipitate well. Under constant stirring, preferably use a mag-
netic stirrer, add 50 ml of 0.5 normal carbonate-free sodium hydroxide through
the funnel and dissolve adhering precipitate. Wash the funnel. Continue with the
stirring until all precipitate has dissolved. Without continuous stirring lumps are
formed, which are dissolved very slowly. Adjust the volume to about 200 ml and
add 7 drops of the mixed indicator. Back-titrate with 0.5 normal hydrochloric acid
until the color changes from violet to grey-bine. Over-titration gives yellow color.
If using an autotitrator, titrate to p~ 8.6.
Carry out a blank exactly as above and use the same volumetric equipment,
only omitting the sample.
Z. analyt. Chem., Bd. 189 17
246 Sylph-ERIc DA~LG~ Bd. 189

Calculation: :p ~ N (a--b). 2.7298, where T ~ mg P205 in the aliquote;

N ~-~ normality of the hydrochloric acid; a --~ hydrochloric aeid consumption for t h e
blar~k, ml; b -~ hydroehloric acid consumption for the sample, ml.
To obtain " p " in mg P, use instead t h e factor 1.1913.
Gravimetric Modifieatlon. W a s h the precipitate 6 times b y decantation using
about 30 ml of water each time. Pour the deeantate into a dried a n d weighed
porcelain filter crucible, fiueness A 3, connected to vacuum. Transfer remaining

I i , T I l , l l l l , r r f 4 , r ~ I I
0 5 /5 20c~
:Fig.1. Aluminium block for heating porcelain filter crucibles. With hole for bimetallic thermometer

precipitate b y means of a water jet. Wash 4 Limes with water and suck dry each
time. Place the crucible into a h e a t e d aluminium block with pits for the crucibles,
see Fig. 1. Kent the block c a a t h e r m o s t a t - or energy-regulated hot-plate.
:Precipitate containing Block t e m p e r a t u r e Retention time
50 mg P205 250--275 ~C 20 minutes
20 mg PsO~ 200--250~ 15 minutes
Cool in a desiccator 45 minutes before weighing.
Carry out a blallk exactly, as above, only omitting the s a m p l e .
Subtract t h e b l a n k from t h e weight of t h e precipitate. Clean t h e crueible with
ammonia 1 : 1.
Calculation: the precipitate contains 3.20730/0 P205 or 1.3998~ P.
Reference Substance. As a reference substance monopotassium dihydrogen
phosphate A R was used. I t was dried 2 h at 105~ cooled in a desiccator, ground
a n d dried another 2 h at 105 ~C. ~ i n l y due to inocculated water, the purity obtain-
able is 99.8 to 99.9%. 4.7936 g of the reference substance was dissolved in water
ad 1000 ml. Each ml therefore gets a nominal content of 2.5 mg P205. The real
content is for reasons declared a little lower.
1962 Simplification of the quinolinium phosphomolybdate method 247

Determination of the Equivalent Point

Precipitate containing 50 mg P205 was dissolved in 42 ml 0.5 normal
sodium hydroxide and diluted to 200 ml. During the back-titration with
0.5 normal hydrochloric acid a
//
titration curve was plotted, Fig. 2. The
inflexion-point is at pH 8.6. pH

Tolerance Limits for Nitric Acid

and Acetone IO
In the systematic study of the
qnimociac method the volumetric
modification was used tt~roughout
with 20.00 ml of the reference solution
with a nominal content of S0 rag P205.
All titrations were done with an auto-
titrator. As a first step the interaction
was studied of the acetone content
and the nitric acid normahty in the
final precipitation solution. Except
for variation of those two ingredients ~.5 5.0 5.5 bT.0
the given procedure was followed. mL 0.5-H HOt
The results are given in Table 1. Fig.2. Potentiometric titration curve of
quinolinium phosphomolybdate dissolved
At too high acetone content, the in sodium hydroxide and back-titrated
acetone is able to dissolve some of with hydrochloric acid

the quinolininm phosphomolybdate,

and at too low acetone content the physical condition of the precipitate
is unacceptable or precipitation incomplete. Too low an acidity results in
incomplete precipitation and too high an acidity in either poor physical
condition of the precipitate, violent reaction of the mixture while heating
or incomplete recovery at high acetone content. The tolerances are con-
siderable for acetone as well as for nitric acid. We choose the acetone level
having the widest nitric acid range, 28 ml of acetone per sample. This is
the same as was used by FERNLUND and Z]~cm~]~ 4. The precipitate
:formed in the lower nitric acid range was somewhat easier to dissolve in
sodium hydroxide, than ff formed in the higher acid range.
The boiling point of the final precipitation solution varies with the
composition. At the nitric acid normality 1.75 the following was ob-
'~ained:
Acetone, ml per sample 10 15 20 28 33 38 43
Boiling point, ~ 85 82 80 75 73 70 65
Tolerance Limits for Citric Acid
Influence of the amount of citric acid in the reagent solution on the
precipitation is given in Table 2. We find t h a t there is a lower limit, below
17"
248 SVE~-E~cDA~mG~E~ Bd. 189

Table 1. Influence o] the Nitric Acid and Acetone Contents in the Quimoeiac Reagent
Solution on the Precipitating Conditions of Quinotinium Phosphomolybdate
The tolerance region is marked
~itrie acid Amount of P205 in mg obtained at varying content of acetone
normality in final 48 ml
precipitation 15 ml 20 ml 24 ml 28 ml 33 ml 38 ml acetone
solution per sample

0,45 46.50 46.38

0,50 49.92 ~ 499:"1 9.74 49.72!
0.55 ! 49.92 49.92 49.92 49.85
0.70 49.92 e I! 49.92 49.92
0.80 : b i 49.92 49.92
0.85 49.92 49.92
0.90 ] 49.92 49.92 49.92 49.92
1.00 I,,.49"92 49.92 49.92 49.92 48.24
1.75 b 49.92 49.92 49.86 49.78
3.60 49.92 49.92 i 49.92 49.58
5.50 49.92r d ..........] 4 9 . 9 2 ,l 49.60 ~ 49.24
I
7.30 I d
a = permanent turbid solution, incomplete sedimentation; h = normal
precipitation, but the precipita, te possesses ur~aecep~able slow sedimentation;
c = normal precipitation, but~ the precipitate is volumiuous and forms lumps,
which are difficult, to dissolve in sodium hydroxide; d ~ violent reaction under
formation of nitrous gases when heated; e ~-~ normal precipitation, but the
precipitate possesses poor filtration properties and forms lumps, which are difficult
to dissolve in sodium hydroxide.

Table 2. Influence o] Citric Acid at Varying Nitric Acid Normalities on the

Precipitation Conditions o/Quinolinium Phosphomolybdate
The tolerance region is marked

g of citric acid mono- Amount of P~O~ in mg obtained at varying nitric acid normalities in the
hydrate per sample final precipitation solution
added through the
reagen~ solution 0.90 n t.25 n 1.75 n 2.00 n 2.50 n

3 a a a a

3.5
4 49.88 a a a

4.5 -- 49.88 a a a

5 49.97 49.90 49.97

13 49,88
14 49.61 49.88 49.92 49.92
15 -- 49.40 49,65 49.93 49.90
16 49.63 49.22
a -~ lumpy, unfilteraTole precipitate.
1962 Simplification of the quinolinium phosphomolybdate method 249

w h i c h t h e p h y s i c a l c o n d i t i o n o f t h e p r e c i p i t a t e is u n a c c e p t a b l e a n d a n
u p p e r l i m i t a b o v e w h i c h p r e c i p i t a t i o n is i n c o m p l e t e . B o t h l i m i t s a r e
increasing at increasing normality of the nitric acid, the upper limit
s o m e w h a t m o r e t h a n t h e l o w e r one.
The chosen 6 g of citric acid per sample 50
is r a t h e r close t o t h e l i m i t i n t h e h i g h rnL I
acidity range. An increase of this amount I
/
would, however, result in a corresponding 4'0
\
smaller tolerance for citric acid in the \

/
a l i q u o t . T h e c h o i c e is t h u s a q u e s t i o n o f \
balance. 30
\
\
Interference of the Ammonium Ion \
and 1)etermann Solution \
When using the Perrin gravimetric
method, the tolerance limit for PETrR-
MAN~ solution is 8 ml in an aliquot con-
20

/0
\ \

taining 50 mg P~05. The precipitation

volume is here 400 ml compared to 200 ml
in the W ~ s o N procedure. I n the latter
case only 4 ml of PET~MAN~r solution is 0 28 38 #0 50
tolerated. B y doubling the precipitation % P205 /~ ~he s~mp/e
~ i g . 3. m l e f PET~R~ANN solution car-
volume 8 ml do not even in this case r i e d over in an aliquot containing
interfere. The limit for addition of ammo- 50 mg P~05from the water and citrate
soluble extract ( ) and from the
nium is only about 100 mg in the Wn~so~ citrate soluble extract ( - -- --) using
method, when added as ammonium the official Swedish method, when the
percentage of P~05in the sample varies
nitrate.

Table 3. Influence o/Petermann Solution at Varying Nitric Acid Normalities on the

Precipitation Conditions o/ Quinolinium Phosphomolybdate
6 g citric acid m o n o h y d r a t e per sample introduced t h r o u g h t h e reagent solution.
The tolerance b o u n d a r y is marked
Amount of PETER- : Corresponding
~ANNsolution extra amount of Amount of P~O5 in mg, obtained at varying nitric acid
added to each citric acid normalities in the final precipitation solution
sample monohydrate
ml g 1.25 n 1.75 n 2.00 n 2.50 n

30 5.2 49.97
35 6.1 49.26
40 6.9 49.97
45 7.8 49.76
50 8.7 22.01 48.39 49.88 49.88
55 9.5 49.61 49.83
60 10.4 49.61
69.4 12.0 47.30
250 SVEN-ERIc DAn%G~]~ Bd. 189

I n Fig. 3 is shown the amount of P~T~RMA~ solution carried over,

when taking an aliquot containing 50 mg P~O5 and extracting according
to the official Swedish procedure for water and citrate solubility and
citrate solubility 9. The tolerance limits in the PERgI~ and WrLso~
methods are thus far too low to be accepted.
Additions of up to 10 g ammonium as ammonium nitrate do not
interfere in the quimociac method. Still higher additions were not in-
vestigated. The tolerance limit for P~T~I~MA~N solution increases at
increasing nitric acid concentration as shown in Table 3. The correspond-
ing amounts of citric acid are a little lower than the limits in Table 2 for
acidities below 2.00 normal. The difference is explained by the neutraliz-
ing effect of ammonium in the P~T~RMAN~ solution. Choosing the nitric
acid normality 2.00 the P ~ T ~ a ~ A ~ solution tolerance will cover all
normal fertilizer mixtures. I f necessary a smaller aliquot is taken.

Interference of Chloride, Perchlorate and Sulfate Ions

Depending on the digestion procedure used in the determination of
total phosphorus, nitric, hydrochloric, perchlorie and sulfuric acids are
introduced.
I n one series of tests the chloride ion was added as a salt in order not
to influence the total acidity and in another series as hydrochloric acid.
Three reagent solutions were used giving a nitric acid normality 0.90;
1.25 and 1.75 in the final precipitation solution. Higher acidities were
obtained b y adding extra acid to the last mentioned prepared reagent
solution. The results are given in Table 4. We find that some of the
findings are too high. The reason for this is t h a t the potassium chloride
used contained about 0.001~ P205, the hydrochloric acid and the extra
nitric acid both about 0.0015~ P205 calculated on anhydrous basis.
Taking those phosphorus impurities into consideration we find t h a t at a
nitric acid normality of 2.50, a potassium chloride normality of 1.0 does
not interfere. At a nitric acid normality of 3.00 the same amount of KC1
gives a weak interference and at nitric acid normality 3.50 the inter-
ference limit of potassium chloride is somewhat less t h a n 0.5 normal. The
determinations a t nitric acid normality 0.90 were made using hydro-
chloric acid from another batch, which did not contain phosphorus. The
interference limit for hydrochloric acid is 1.35; 1.25 and 1.00 normal at
nitric acid normalities 0.90; 1.25 and 1.75 respectively. The chloride
interference limit thus decreases at increasing nitric acid content in the
reagent solution and neutralization widens the limit somewhat.
I n Table 5 the interference of suffurie and perehlorie acids on the pre-
cipitation is given. At nitric acid normality 2.00 a suffuric acid concentra-
tion up to 2 normal is tolerated. The interference limit for perchloric acid
is 1.60 and i.00 normal at nitric acid normalities 0.90 and 2.00 respectively.
1962 Simplification of the quinolinium phosphomolybdate method 251

Table 4. Inter/erence o/ the Chloride Ion on the Precipitation

Chloride ion Nitric acid normality in Chlorideion normality in Amountof P205 obtained,
added as final precipitation solution finalprecipitation solution in mg

1.75 0 49.90
1.75 0.5 49.97
1.75 1.0 50.04
2,50 0,5 50.10
KCI 2.50 1.0 50.17
3.00 1.0 50.04
3.50 0.5 50.17
3.50 0.75 49.97
3.50 1.0 49.35

0.90 1.10 49.91

0.90 1.35 49.88
0.90 1.60 49.59
0.90 2.10 22.89
0.90 2.60 0
HC1 1.25 1.25 50.04
1.25 1.50 48.81
1.25 2.00 18.73
1.75 1.00 49.97
1.75 1.25 48.60
1.75 1.56 36.70
1.75 3.12 0

Table 5. Inter[erence o/the Sul]uric and Perchloric Acids on the Precipitation

Addition Nitric acid
normality in Amount of
normality in precipitation P20~ obtained Remarks
~S precipitation solution
solution mg

I-I2SO4 2.00 2.00 49.88 OK

2.50 2.00 49.47
3.00 2.00 44.54
HCI04 1.60 0.90 49.96 OK
2.10 0.90 49.81 preeipibate sticky
2.60 0.90 49.81 precipitate sticky
1.00 2.00 49.88 OK
1.25 2.00 49.81 poor filterability
1.50 2.00 49.83 poor filterability
1.75 2.00 49.83 poor filterability

T h e i n t e r f e r e n c e l i m i t s for t h e s e acids a r e sufficient for f e r t i l i z e r

applications at the nitric acid normality recommended. For other appli-
c a t i o n s , w h e r e t h e c i t r i c a c i d is n o p r o b l e m , a c o n s i d e r a b l y l o w e r n i t r i c
a c i d n o r m a l i t y c a n be c h o s e n a n d c o r r e s p o n d i n g l y h i g h e r i n t e r f e r e n c e
l i m i t s for t h e o t h e r m i n e r a l acids o b t a i n e d .
252 SvnN-E~Ic ]).~GR~N Bd. 189

Interference ot Silica
Citric acid in the reagent solution has been shown to be necessary to
obtain a suitable physical condition of the precipitate. The primary
reason was, however, to eliminate silica interference. Silica has been
added as quartz fused in soda and as fluosflicic acid to samples of known

Table 6. Inter]erence e] Silica at Volumetric

Determination Table 7. Inter[erence o/ Silica at Gravl-
Nitric acid normality 2.00 in ehe final metric Determinativn. Silica added as
precipitabion sotu~ion quartz ]used with sodium carbonate
Nitric acid normality 2.00 in the final
Silica added Amount of precipitation solution
m g SiC2
P~O~ obtained
a,~
per sample nag l~elative deviation of P20~
mg SiOa obtained compared with
Quartz fused 200 49.91 per sample silica-free sample
~
wi~hN%COa 300 49.95
400 50.23 100
i

[ + 0.02
~2SiF 6 200 49.91 200 t + 0.04
250 49.88 300 + 0.14
300 50.20

phosphorus content. With the reagent solution 6 g of citric acid per

sample were introduced. From Tables 6 and 7 we find t h a t per 50 nag
P~O~, 200--250 mg Si02 can be tolerated. This is enough for all fertilizer
applications. At the determination of total phosphorus the silica can, ff
necessary, be made insoluble by the usual acid evaporation to dryness.

Hydrolysis of Non.0rthophosphates
In the common phosphorus fertilizers only a minor part of the
phosphorus is present as non-orthophosphates. To obtain a correct result
and a good reproducibility, it is necessary to hydrolyze this part into
orthophosphate b y simmering in a mineral acid solution. In this study
15 ml of cone. nitric acid sp.g. 1.40 were added to each aliquot and a
corresponding decrease of the amount of acid in the reagent solution was
made. Thus the acidity of the final precipitation solution was not changed.
The gravimetrie procedure was used.
The hydrolysis of ~etrasodium pyrophosphate AR, sodium tripoly-
phosphate technical grade, single and triple superphosphate, N P K 7-7-14
and P K 15-15 was studied. For each test an aliquot containing about
50 mg P~O~ was taken, with the exception of the last two, where about
30 and 40 mg P~05, respectively, were taken. This was necessary in order
to keep the specified volume at the precipitation. Extraction of the ferti.
lizers was done according to the official Swedish procedure for water and
citrate solubility 9.
1962 Simplification of the quinolinium phosphomolybdate method 253

Table 8 illustrates that the presence of PETER~A~ solution decreases

the rate of hydrolysis. For sodium tripolyphosphate the required sim-
m e r i n g t i m e w a s i n c r e a s e d f r o m 4 - - 1 5 r a i n . T h e h y d r o l y s i s o f t h e fer$i-
Table 8. Hydrolysis o/Tetrasodium Pyrophosphate A R and Sodium Tripolyphosphate
Technical Grade
Total solution volume 75 ml
Amount of Amount of P20s obtained.
Salt 1)ETER~[ANb!solution Simmering time l~elative deviation from
ml minutes correct value in per cent

Tetrasodium 0 2 -- 0.14
pyrophospha~e 0 3 0
0 15 O
40 1 -- 6.94
40 3 -- 0.54
40 4 -- 0.28
40 5 0
Sodium tripoly- 0 1 -- 0.73

phosphate O 2 - - 0.28
0 3 -- 0.14
0 4 0
0 15 0
40 5 -- 0.65
40 10 -- 0.37
40 15 0
Table 9. Hydrolysis o/some Phosphate Fertilizers, Extracted According to the O/]icial
Swedish Procedure/or Water and Citrate Solubility
Amount of P20s obtained.
Fertilizer type Simmering time Relative deviation from correct
minutes value in per cent

Single no heating -- 0.07

Superphospha~e 10 -- 0.01
15 0
Triple no heating -- 6.01
Superphosphate 5 -- 0.01
very h a r d dried 15 0
NPK 7--7--14 no heating -- 0.22
5 -- 0.13
15 0
PK15--15 no heating -- 0.14
5 -- 0.14
15 0

lizer s a m p l e s is r a t h e r slow, as s e e n i n T a b l e 9. T o b e o n t h e safe side i t is

r e c o m m e n d e d t o h y d r o l y z e f o r 15 m i n , w h e n d e a l i n g w i t h c i t r a t e e x t r a c t s .
For other applications the required time can in many eases be shorter,
b u t h a s t o b e e s t i m a t e d i n e a c h p a r t i c u l a r case.
 254 SvE~-Ealc D A n ~ o ~ Bd. 189

Gravimetric Modification
A thermogravimetric study of the quinolinium phosphomolybdate by
WE~DLA~DT and HOF~MA~1~ showed that its monohydrate is stable up
to 107~ Weight stability was obtained from 155--370~ Dehydration
of the precipitate is made considerably faster b y using a heated aluminium
block than by using an oven. Details have been given under Procedure.
The anhydrous precipitate is somewhat hygroscopic as shown by Fig. 4.
No special precaution need, however, be taken.
In semi-micro determination, F E ~ L L and WEBB a removed remain-
ing water in the precipitate by dioxane and then washed with ether. The
precipitate could be weighed 5 rain after sucking dry. I f heated, the preci-
§ pitate lost slightly more than
m~ / 2 moles of water per mole of
§ ~,~ quinolinium phosphomolybdate.
__ J Their drying technique has here
been applied to macro deter-
_~+ 3 - - J minations. Precipitate contain-
__ ing 50 mg P~05 was after the
y water wash, washed 3 times,
each with 10ml of dioxane
followed b y 3 alternatively 6
o washes each with 10 ml of ether.
b Finally sucking dry for 5 min.
-/ Methanol and ethanol could not
0 O.Y 1.0 15 2.0 2.5 d.O d..5
Exposure hme. b. be used to remove water, as they
Fig.4, Moisture pick-up of anhydrous quinolinium dissolvedsomeoftheprecipitate.
phosphomolybdate containing 50 mg P~0~ after The weight of the precipitate
45 minutes cooling in a desiccator, when exposed in
air with 58~/0 relative humidity, i mg weight change 5 rain after sucking dry was not
equal to 0.064V0 relative error. Curve a: crucible + reproducible. When exposed to
precipitate; curve b: empty crucible
air at room temperature with a
relative humidity of 35~ for 6 hrs, a constant weight was obtained and the
composition corresponded to dihydrate ofquinolinium phosphomolybdate.
At a higher humidity an unconstan~ but higher weight was obtained within
24 hrs and at a lower one an unconstant but lower weight was obtained
within the same period. The weight loss as a function of the time showed
a hold-up at the dihydrate composition in the latter case. These findings
indicate the existence of a dihydrate. Owing to the long time and the
narrow conditions to obtain this, it has no analytical interest. Only the
high temperature drying to anhydrous state, earlier described, is of
practical use.
Discussion
The primary object of this investigation has been to find a modifica-
tion of the quinolinium phosphomolyhdate method that is generally
 1962 Simplificationof the quinolinium phosphomolybdate method 255

applicable to the analysis of fertilizers. For other applications, where

there are no complications with citric acid (ammonium citrate), it is
recommended to use a lower nitric acid normality at the precipitation, as
this widens the tolerance limits for other mineral acids. The reagent solu-
tion recommended under "Hydrolysis of Non-Orthophosphates" gives
on its own a nitric acid normality of 0.90 in the final precipitation solu-
tion. This is expected to be suitable for these other applications.
The wide tolerance limits for different impurities and chemicals intro-
duced during the analysis, indicate that the presented method can find
application in many fields. I f the chemicals introduced during the analy-
sis, e.g. ammonium citrate, contain traces of phosphorus, they must be
included in the blank in the same amounts as those transferred with the
aliquot of the sample solution. Otherwise too high results are obtained.

Summary
For application on fertilizer analysis a serious drawback of the
qninolinium phosphomolybdate method has been its susceptibility to
interference by ammonium. The introduction of acetone in the reagent
solution has completely eliminated this interference and at the same
time involved a considerable simplification of the analytical technique.
There are wide tolerances for the presence of citric, sulfuric, nitric, hydro-
chloric and perchloric acids as well as for silica. The method has been
given one volmnetrie and one gravimetrie modification.

Zusammenfassung
Die Verwendung der ChinolJn-Phosphomolybdat-Methode fiir die Ana-
lyse yon Diinger war bisher mit einem grogen Nachtefl verbunden, niimlich
der St6rung dutch Ammonium. Diese St6rung ist dutch die Benutzung
von Aeeton in der Reagensl6snng v611ig beseitigt worden. Gleichzeitig war
eine bedeutende Vereinfachung in der Ausfiihrung der Analyse m6glich.
Es gibt breite Toleranzgrenzen fiir die Anwesenheit von Citronens/~ure,
Schwefcls~ure, Salpeters/iure, Salzsgure, Perehlors/iure und Kieselsgure.
Man hat der Methode eine volumetrische und eine gravimetrische Aus-
ffihrung gegeben.
Acknowledgement. Sincere thanks are due to BERN]~)~gDSS~tNS,who carried
out most of the experimental work, and to KORNELtIORV~Ttt, who at a later stage
joined the team, for their great interest and careful work.

References
1 ALFELT, G. : Jernkont. Ann. 148, 167 (1959). -- e I)UTTA,A.N., and N. GUF~A:
Indian J. appl. Chem. 22, 9 (1959). -- s FENNELL,T. R. F. W., and J. R. WEBB:
Talanta (London) 2, 105 (1959); cf. Z. analy~. Chem. 173, 314 (1960). -- a FERN-
LVND,U., and S. ZEC~NER: Bestimmung yon Phosphor in Eisenerz, unpublished
manuscript, Loussavaara-Kiirnnavaara AB, Kiruna C, Sweden. -- 5 FE~NL~]), U.,
and S. ZEC~NE~:Z. analy~. Chem. 146, 111 (1955). -- 6 FER~LU~D,U., S. Z]~c~,R
256 H~AnD Rf~SSEL Bd. 189

and T. AiVDERSSON:Z. ~n~lyt. Chem. 188, 41 (1953). -- ~ F ~ L U N D , U., S. Z]~CH-

N ~ and S.-0. ERI~SSO~V: Jernkont. Ann. 140, 389 (1956). -- s FnR~VND, U.,
S. ZEe~NER and i%. OnOFSSON: Jernkont. Ann. 140. 386 (1956). -- ~ Kungl.
Lantbruksstyrelsens KungSrelser Nr 7, Stockholm 1950. -- ~0 PERRI~V,C. H.:
J. Assoc. off. ag~ic. Chemists 41, 758 (1958); cf. Z. analyt. Chem. 169, 289 (1959). --
n PER~n% C. H.: J. Assoc. off agric. Chemists 42, 567 (1959); cf. Z. analyt. Chem.
177, 138 (1960). -- x~ Statutory Instruments 1960, No 1165. The Fertilizer and
Feeding Stuffs Regulations, 1960. Her Majesty's Stationery Office. -- ~ W ~ D -
LA~D~, W. W., and W. M. HologrAm: Analy~. Chemistry 82, 1011 (1960); cf. Z.
analy~. Chem. 180, 48 (1961). - - ~ ~V~Lso~, H. N.: Analys~ 76, 65 (1951). - -
~s Wmso~, H. N.: Analyst 79, 535 (1954); el. Z. an~ly~. Chem. 147, 371 (1955). - -
~ Znc~n~., S., and V. t~P~nSTA~: Z. an~lyt. Chem. 163, 423 (1958).
SvE~-E~c D~LG]~S~, )Ianager l~esearch and Development Department,
AB FSrenade Superfosfatfabriker, Landskrona (Sweden)

Aus der Bmldesans~al~ fiir Bodenforschnng in H~nnover

Polarographische Bestimmung kleiner Mengen Wismut

in Gesteinen und Erzen
Von
~i~ARALDROSSEL *
(Eingegangen am 15. Februar 1962)

Die B e s t i m m u n g kleiner Mengen W i s m u t erfolg~ m e i s t spek%ral-

photome~risch m i t d e n R e a g e n t i e n Thioharnstoff, K a l i u m j o d i d oder
Dithizon. Diese V e r f a h r e n h a b e n d e n N a c h t e i l , dal3 die R e a g e n t i e n
n i c h t spezifiseh u n d z u m Teil auch wenig empfindlich sind. Ffir die zu
e n t w i c k e l n d e U n t e r s u c h u n g s m e t h o d e w a r e n folgende F o r d e r u n g e n auf-
gestellt w o r d e n :
1. Es mu8 noch 1 #g Wismut mi~ einer Abweichtmg yon nieh~ mehr als 20%
bes~imm~ werden, bei ~Iengen fiber 100/~g Bi darf die Abweiehtmg nieh~ mehr
als 10~ be~ragen.
2. Eine Person mug ti~glieh mmdes~ens 10 Analysen bew~Itigen k6nnen.
3. Stbrungen dutch andere Elemente diirfen nicht aufi;re~en.
A u f G r u n d dieser F o r d e r u n g e n erschien uns die Messung m i t d e m
K a t h o d e n s t r ~ h l p o l ~ r o g r a p h e n a m geeignetsten, d e n n sie 1/~J3tsioh sehnell,
genau, his a u f 0,5/~g h e r a b u n d m i t grol~er S i e h e r h e i t durchffihren.
(Aueh eine H i l f s k r a f t k a n n erkennen, ob das E r g e b n i s d u r c h die benaeh-
b ~ r t e Stufe eines a n d e r e n E l e m e n t e s beeinflufit w u r d e odor nieht.) Als
G r u n d l 6 s u n g w u r d e saure T a r t r a t l 6 s u n g n a c h LmG~-~E s sowie Swx~E.
HART, GAt~:ETT U. MACN:EYER~N4 einer 2 n S a l p e t e r s s vorgezogen
9 ~[ehlem hochverehr~n Lohrer ProL GOVB:~Avzum 60. Gebur~te,g gewidme~.