In the Laboratory
Determination of Phosphates
by the Gravimetric Quimociac Technique
Lee Alan Shaver
Department of Chemistry, Washburn University, Topeka, KS 66621; alan.shaver@washburn.edu
Many gravimetric methods of analysis performed by
students are tedious, laborious, and may not be in wide use in
non-academic laboratories. However, students acquire improved
laboratory technique skills and learn interesting chemistry
from experiments involving gravimetric methods. Laboratories
throughout the world utilize the gravimetric technique when
relatively high accuracy and precision are required.
Phosphates are commonly found in fertilizers, cleaners,
cement, and as food and feed additives. Some phosphorus-
containing compounds such as phosphorus sulfides are com-
monly processed into lubrication oil additives, pesticides, and
ore flotation products. Rapid, simple, accurate, and precise
phosphorus-content results are required for the production and
sale of many of these compounds (1, 2).
The so-called gravimetric quimociac technique is a classic
method proven to meet this need in industrial and government
labs. It has worked very well as an experiment in our under-
graduate analytical chemistry laboratory. The term “quimociac”
is the shortened name for the quinoline molybdophosphoric
acid precipitate formed in the test method. The method has
the advantages of producing a predictable, stable, high molar
mass precipitate that students find easy to form, filter, dry, and
weigh.
The group of students performing this experiment enjoyed
it much more than the groups doing the more tedious classic
filtration of gelatinous iron hydrous oxide in the gravimetric
determination of iron listed by Harris (3).
Principle
This method consists of first converting all the phosphorus-
containing species in the sample to soluble orthophosphate
(PO43‒) ion by oxidation and hydrolysis in acid solution. Then
an acidic quimociac reagent is added to the prepared orthophos-
phate sample and a bright yellow precipitate forms. The resulting
precipitate is filtered, dried and weighed. Precipitation follows
the reaction:
Validation of the gravimetric quimociac method was the
subject of several studies, especially for fertilizer analysis (7, 8).
This is a good opportunity to introduce students to the
interesting chemistry involved in the gravimetric quimo-
ciac method. In acidic solutions, molybdate ions react with
orthophosphate ions to form the classic heteropoly cage-like
Keggin structure of 12-molybdophosphate (9–11). Twelve
molybdate ions surround a single phosphate ion (Figure 1). This
heteropoly anion accepts three acidic protonated quinoline cat-
ions to form the insoluble quinoline molybdophosphoric acid.
Experimental
The quimociac reagent is prepared a day or more in
advance. Ammonium molybdate tetrahydrate is dissolved in
deionized water. In a separate beaker citric acid monohydrate
is dissolved in dilute nitric acid. After cooling, the molybdate
solution is added to the citric–nitric acid mixture with agitation.
In a separate beaker, synthetic quinoline is added to deionized
water. Then the quinoline solution is added to the molybdate–
citric–nitric acid solution. After mixing, the solution is allowed
to stand overnight. The solution is filtered through fine porosity
paper then acetone and deionized water are added. Then the
solution is mixed and stored in a polyethylene bottle. The mixed
reagent is generally stable for up to one month.
Sample preparation depends on the type of sample of
material to be tested and may be done in advance. Students
may be provided with both known and unknown samples. For
example, solid inorganic phosphates are oven dried overnight a
day or more in advance to remove moisture. For typical samples
of this type, between 0.5 to 1 g of sample is weighed to the
nearest 0.1 mg. The sample is transferred to a beaker; deionized
water is added, along with concentrated nitric and hydrochloric
H3PO4  12H2MoO4  3C9H7N

(C9H7N)3·H3PO4·12MoO3·H2O  11H2O

When the precipitate is dried, the water of hydration is removed,

leaving a stable, anhydrous, yellow product with a molar mass
of 2213 g/mol (4).
It is essential to convert all the phosphorus in the sample
to soluble orthophosphate (PO43‒) ion. Examples of treatments
are oxidation and hydrolysis by heating in acidic bromine or in
nitric acid solution. Inorganic polyphosphates (pyro-, tripoly-,
and glassy phosphates) are hydrolyzed to orthophosphate by
boiling in acid solution.
Citric acid and acetone are added to the quimociac reagent Figure 1. Cage-like Keggin structure of 12-molybdophosphate acid:
to eliminate interference from silicate and ammonium ions, the orange circle is the P atom; the pink circles are the Mo atoms;
respectively, that are present in some types of samples (5, 6). and the red circles are the O atoms.

© Division of Chemical Education  •  www.JCE.DivCHED.org  •  Vol. 85  No. 8  August 2008  •  Journal of Chemical Education 1097
 In the Laboratory
acids. The beaker is covered with a watch glass and the solution
is boiled gently on a hot plate in the fume hood for about 15
minutes (one hour for glassy phosphates or phosphate rock).
More deionized water is added if necessary so that the solution
does not go dry. The solution is cooled, filtered if necessary, then
transferred quantitatively to a volumetric flask. The prepared
sample solution is then diluted to volume with deionized water
and mixed.
Sample analysis is normally completed during the sched-
uled lab period. An aliquot of the prepared sample solution
containing up to 70 mg as P2O5 is quantitatively transferred
by pipet to a beaker then diluted to about 100 mL with deion-
ized water. Quimociac reagent is added to the sample solution
with gentle swirling. The beaker is covered with a watch glass
and heated to a boil for one minute. At this time a yellow pre-
cipitate forms. The solution is cooled in a water bath to about
room temperature, then vacuum filtered through a clean, dry,
tared, medium-porosity fritted-glass filter crucible. The yellow
precipitate is washed with small portions of deionized water. The
precipitate on the fritted-glass filter is dried for 20–30 minutes
at 200–230 °C. The crucible containing the precipitate is cooled
in a desiccator then weighed to the nearest 0.1 mg.
The fritted-glass filter crucibles may be cleaned before
and after the test by brief soaking in 10% sodium hydroxide or
concentrated aqueous ammonia followed by dilute acid and
water rinses. The crucibles are dried at 200–230 °C for an hour
or more then cooled and stored in a desiccator. The heated and
cooled crucibles are weighed then heated and cooled again until
a constant weight is obtained.
Calculations are relatively simple and it is a good exercise
for the students to compute the molar mass of the precipitate
from the stoichiometry given in the precipitation reaction then
set up the calculation equation. It is common practice to report
phosphorus content either as percent of P2O5 or as percent of
P. The calculation for percent of P2O5 is
g sample
mass ppt 141 . 9 volume 100%
mol P2 O 5 ratio
percent
P2O5 
g mol ppt mass
22213 2 6. Dahlgren, S. E. Z. Anal. Chem. 1962, 189, 243–256.
mol ppt mol P2 O5 sample
sample
volume sample solution
volume  9. Pope, M. T. Heteropoly and Isopoly Oxometalates; Springer-Verlag:
ratio volume sample aliquot
Hazards
Nitric and hydrochloric acids are corrosive and dangerous
if inhaled or if they come into contact with any part of the body.
Quinoline, citric acid, acetone, and ammonium molybdate are
all irritants. Quinoline is a cancer suspect agent. Acetone is vola-
tile, flammable, and dangerous if inhaled. Work in the hood and
wear protective gloves when preparing the quimociac reagent
and when treating samples with acids. Sodium hydroxide and
aqueous ammonia are irritants. Aqueous ammonia is an inhala-
tion hazard and should be used in the hood.
Student Results
Overall student results were within 6% (relative) of certi-
fied values and the relative standard deviation was less than
1098 Journal of Chemical Education  •  Vol. 85  No. 8  August 2008  •  www.JCE.DivCHED.org  •  © Division of Chemical Education
3%. The unknowns that the students tested contained 10 to
11% P2O5. This accuracy and precision are typical for samples
containing this level of P2O5 when compared to the results of a
collaborative study where multiple analysts tested 29 different
samples ranging from 0.02 to 61% P2O5 (12). The greater the
percent of P2O5, the better the accuracy and precision. Accuracy
and precision also improve with experience.
One sample can be analyzed in about two hours, of which
25 minutes is working time. Six samples can be analyzed in about
three hours, of which one hour is working time. The quimociac
reagent and filter crucibles need to be prepared prior to the
laboratory session. Samples may need to be dried and prepared
in advance.
Summary
Reported here is a practical, accurate, and precise gravi-
metric technique for the determination of phosphates as a lab
experiment for undergraduate analytical chemistry laboratories.
The experiment requires some preparation of reagents and
samples in advance, but students should find it easy to complete
the lab within a single three-hour lab period. In addition to
practicing laboratory gravimetric technique, students should
also learn about the dissolving and hydrolysis of phosphate-
containing compounds as well as the formation and structure
of 12-heteropoly molybdophosphoric acid.
Literature Cited
1. Hoffman, W. M.; Ferretti, R. J. J. AOAC Int. 1962, 45, 40–46.
2. Solomon, S.; Lee, A.; Bates, D. J. Chem. Educ. 1993, 70,
410–412.
3. Harris, D. C. Quantitative Chemical Analysis, 7th ed.; W. H.
Freeman and Company: New York, 2006; Experiment 3 from
text Web site; http://www.whfreeman.com/qca7e (accessed Mar
2008).
4. Wendlandt, W. W.; Hoffman, W. M. Anal. Chem. 1960, 32,
1011–1012.
5. Wilson, H. N. Analyst 1954, 79, 535–546.
7. Hoffman, W. M.; Breen, H. J. J. AOAC Int. 1964, 47, 413–419.
8. Johnson, F. J. J. AOAC Int. 1973, 56, 1084–1086.
New York, 1983; pp 23–31.
10. Moffat, J. B. Metal-Oxygen Clusters; Kluwer Academic/Plenum
Publishers: New York, 2001; pp 5–40.
11. Cotton, F. A.; Wilkinson, G.; Murillo, C. A.; Bochmann, M.
Advanced Inorganic Chemistry, 6th ed.; John Wiley and Sons:
New York, 1999; pp 920–945.
12. Caudill, P. R. J. AOAC Int. 1969, 52, 587–592.
Supporting JCE Online Material
http://www.jce.divched.org/Journal/Issues/2008/Aug/abs1097.html
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Student handout including laboratory questions
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