GRAVIMETRIC DETERMINATION OF PHOSPHORUS

IN FERTILIZER SAMPLES


RESULTS AND DISCUSSION

More than 50% of fertilizers are composed of
nitrogen, phosphorus and potassium because these
three nutrients are essential but are deficient in soils.
To ensure good quality of fertilizers, it is significant
that the amounts of these nutrients are quantified. In
this light, gravimetric principles are of much use [1].

The objective of the experiment is to
determine the percentage of phosphorus and
diphosphorus pentoxide in fertilizer samples.
Gravimetric analysis follows only a few fundamental
steps. Here, the quantity of the analyte is determined by
separating it physically from the system. To do this, it
should be converted to an insoluble substance.
In the experiment, the phosphorus of the fertilizer
sample was precipitated as magnesium ammonium
phosphate hexahydrate [1]. It follows the equation,

5H2O(l) + HPO4
2-
(aq) + NH4
+
(aq) + Mg
2+
(aq) + OH
-
(aq)
MgNH4PO4 6H2O(s) (1) [1]

The precipitating reagent used was ammonia, NH3.
Ammonia is used instead of ammonium chloride
because the latter produces Cl
-
ions that may react with
the Mg
2+
ions found in the solution, thus,
forming MgCl2(s). This can interfere to the production
of the desired precipitate.

Forming the precipitate is critical. First and
foremost, the precipitate formed should be free from
impurities. Also, the size of the particles making up the
precipitate should be considered. In gravimetric
analysis, relatively few crystals are preferred over many
small ones. Experimentally, it was found that particle
size is affected by experimental variables such as
precipitate solubility, reactant concentrations in the
precipitating solution, the rate of addition and mixing
of reactants, and the temperature [2]. Mathematically,
it is reflected in the Von-Weirman ratio which states
that,

(2)[2][3][4]
where Q is the concentration of mixed reactants before
precipitation and s is the solubility of precipitate at
equilibrium. This ratio is the measure of relative
supersaturation [2]. A lower ratio is preferred over a
higher one since it yields larger and fewer crystals, thus,
small surface area. For optimum results, conditions
need to be adjusted such that Q will be as low as
possible and s will be relatively large compared to it [3].
In order to achieve this, Q must be kept low with the
use of dilute solutions, slow addition of reactants, and
stirring the mixture thoroughly [3][4]. Meanwhile, to
ensure a high s, precipitation must be done at high
temperature [3][4], at a pH near the acidic end of the
pH range in which the precipitate is quantitative[3],
and by cooling the mixture after the formation of
crystals [4].

In the experiment, after dissolving the sample
with distilled water, it was then filtered in order to
obtain a clear filtrate. MgSO47H2O was then added to
the filtrate. After which, with constant stirring of the
solution, NH3 was slowly added to the mixture-
forming a white precipitate. Then, digestion, a process
which involves letting the precipitate to stand in
contact with the mother liquor for a certain period of
time, was done to dissolve small particles and grow
larger ones [4]. These steps were done to lower the
concentration of the mixed reactants, Q.

After the digestion process, the precipitate
was transferred quantitatively to the pre-weighed filter
paper. After washing it with (2) 5-mL portions of
distilled water, the precipitate was then washed with (2)
10-mL portions of 95% ethanol. Washing was done to
remove the mother liquor from the precipitate and
force the coagulated colloidal particles apart, causing
them to go right through the filter. Specifically, ethanol
was used because it is of volatile electrolyte and so, it
will be easily removed in the drying step.

The next step was drying or ignition. The
filter paper containing the precipitate was then spread
on a watch glass and stored in the locker until the next
period. On the next meeting, the filter paper was placed
in the oven set at 110C for 1 hour. Before weighing, it
was first cooled for 15 minutes inside a dessicator.

With the acquired data, the percentage of
diphosphorus pentoxide in the fertilizer sample was
calculated using the equation,

(3)

while the calculation of %P used the concept of
gravimetric factor,

(4)

where a,b are small whole numbers that have values
such that the number of formula weights in the
numerator and denominator are chemically equivalent.

The table below shows the calculated values
of %P and %P2O5, both on wet and dry basis, and the
average %P2O5 as well.

Table 1. Calculated values for %P, %P2O5, and average
%P2O5
Trial 1 2
%P (wet basis) 9.22 0.0003 11.10 0.0003
%P (dry basis) 9.35 0.0004 11.42 0.0004
%P2O5 (wet basis) 21.14 0.0007 25.46 0.0007
%P2O5 (dry basis) 21.43 0.0005 26.21 0.0005
Average 23.82 0.0006

It is possible that errors were committed in
this experiment and these lead to erroneous results.
One possible source of error is the abrupt adding of
NH3 solution to the filtrate. This would lead to a higher
concentration of mixed reactants which would
consequently yield a higher ratio of relative
supersaturation, thus, lowering %P.

Another source of error would be failing to
quantitatively transfer the precipitate to the pre-
weighed filter paper. It is possible that some particles
were left in the beaker and so, a lower %P would be
calculated as well. Aside from these, it is possible that
some of the precipitate fell off the filter paper during
the transfer from locker to oven, oven to dessicator,
and from the oven to the analytical balance. Remember
that by that time, the precipitate has dried completely
and can be easily carried by the wind. With this, the
weighed sample would be less than the actual amount
of sample and therefore, %P would be less than
expected.




REFERENCES

[1] Institute of Chemistry. Analytical Chemistry Laboratory
Manual. University of the Philippines Diliman. 2007. p.
27.

[2] Skoog, et al. Fundamentals of Analytical Chemistry,
Eighth Edition. Brooks/Cole Thomson Learning.
2004. p. 316.

[3] Anonymous. Gravimetric Analysis. Retrieved last 18
July 2013 from
http://www.chem.tamu.edu/class/majors/tutorialnote
files/gravimetric.htm.

[4] Anonymous. Gravimetric Analysis and Precipitation
Equilibria. Retrieved last 18 July 2013 from
http://emp.byui.edu/ZAUGGN/Chem220/Powerpoi
nts/Lecture6.ppt.

[5] D.C Harris. Quantitive Chemical Analysis, 8
th
ed. New
York. W.H. Freeman and Company. 2007.