GRAVIMETRIC DETERMINATION OF MOISTURE AND PHOSPHORUS

IN FERTILIZER SAMPLES


M. DAMGO
DEPARTMENT OF CHEMICAL ENGINEERING, COLLEGE OF ENGINEERING
UNIVERSITY OF THE PHILIPPINES, DILIMAN, QUEZON CITY, PHILIPPINES
DATE PERFORMED: AUGUST 29, SEPTEMBER 3, 10 & 12, 2014
INSTRUCTORS NAME: COLLEEN MARCIEL ROSALES



ABSTRACT

The experiment entitled Gravimetric Determination of Moisture and Phosphorus in Fertilizer
Samples aimed to determine the moisture and phosphorus content of a fertilizer sample using the
concepts of gravimetric analysis. In the first part of the experiment, the moisture content was
determined through constant weighing of the empty crucible and the dried crucible with fertilizer
sample. In the second part, the phosphorus content was determined through the weight of
magnesium ammonium phosphate, MgNH4PO4, which was precipitated from the reaction of the
filtrated fertilizer sample mixed with magnesium sulfate heptahydrate, MgSO47H2O, and ammonia,
NH3. The moisture content was found to be 1.28% while the phosphorus content calculated for %P
and %P2O5 were10.977% and 25.155%, respectively, on wet basis and 11.120%P and 25.481%P2O5
on dry basis. It was concluded that the fertilizer sample was of good quality since it contained low
moisture and high phosphorus content, which is more than the standard 20% P2O5 content.


INTRODUCTION

Gravimetric analysis is a technique
through which the amount of an analyte (the
ion being analyzed) can be determined
through the measurement of mass. It can then
be further classified into two: volatilization
and precipitation. In precipitation, the analyte
is separated by converting it into soluble
precipitate. In volatilization, the analyte is
volatilized at a suitable temperature and
collected and weighed.
[1]
Gravimetric
analyses depend on comparing the masses of
two compounds containing the analyte. The
principle behind gravimetric analysis is that
the mass of an ion in a pure compound can be
determined and then used to find the mass
percent of the same ion in a known quantity
of an impure compound.

Gravimetric analysis makes use of the
concept of constant weighing. Since all solids
have a certain affinity for water and may
absorb moisture from the laboratory air, a
sample has to be dried to a constant,
reproducible weight. It is expected to have a
constant weight after a series of heating and
cooling processes.
[2]
This technique can be
used to determine the moisture content of a
solid sample specifically, fertilizer.

Fertilizer samples are comprised
mostly of soluble compounds namely:
nitrogen, phosphorus, and potassium. These
compounds are used to replenish nutrients in
the soil and to increase plant growth. The
amount of these compounds in a fertilizer
sample can be obtained using the fertilizer
grade.

Fertilizer grade is an expression
referring to the legal guarantee of the
available plant nutrients expressed as a
percentage by weight in a fertilizer. A pack
with the label NPK 15-20-15 means that the
fertilizer is composed of 15%N, 20%P
(expressed as P2O5), and 15%K. Analysis of
nutrients and moisture content is essential to
ensure the quality of the fertilizer sample.
Fertilizers are considered good when they
contain low moisture content. Having high
moisture content decreases the quality of the
fertilizer and affects the growth of the plant.
[3]


The first part of the experiment
focused on the moisture content
determination of the fertilizer sample by the
use of constant weighing.

The second part, however, aimed to
determine the phosphorus content of the
sample. The water-soluble phosphate was
precipitated using magnesium phosphate
hexahydrate and given by the equation:

5 H2O + HPO4
2-
+ NH
4+
+ Mg
2+
+ OH
-

MgNH4PO4 6 H2O(s) (1)

The phosphorus content, in the form
of %P and %P2O5, was determined using the
gravimetric factors.

METHODOLOGY
Part 1. Gravimetric Determination of
Moisture in Fertilizer Samples

A. Preparation of Crucibles

One crucible and cover to be used for
drying of the precipitate was washed and
cleaned and placed in the oven set at 110C.
It was kept there until the next laboratory
period.

B. Constant Weighing of Cubicles

Using a pair of crucible tongs, the hot
crucible with cover was transferred into a
desiccator. The desiccator was left to cool at
the balance room. Without opening the cover,
the weight of the crucible was then obtained.
It was transferred back to the oven to dry for
30 minutes with the cover slightly ajar.

The cooling and heating process was
repeated until a constant weight was
obtained.

C. Moisture Analysis

About 3.0g of fertilizer sample was
weighed using the constantly weighed
crucible. With the cover ajar, the crucible
with sample was then placed in the oven to
allow evaporation of vapor. It was then
transferred in a desiccator and cooled in the
balanced room. Without opening the cover,
the weight of the crucible with sample was
taken. The crucible and sample was then
reheated at the oven for 30 minutes. The
process was repeated until constant weight
was obtained.

Part 2. Gravimetric Determination of
Phosphorus in Fertilizer Samples
A. Preparation of Solutions

In the preparation of the 10%
MgSO47H2O solution, 50.0 g of solid
MgSO47H2O was weighed. It was dissolved
and diluted in a 500-mL volumetric flask
using distilled water.

For the preparation of the 2M NH3
solution, 67.6 mL of concentrated (14.8M)
NH3 was transferred into a 500 mL
volumetric and diluted to mark using distilled
water. The process was done three times.

B. Precipitation of MgNH4PO46H2O
A filter paper was prepared and weighed
a meeting prior to the experiment. The
fertilizer sample obtained from Part 1 was
quantitatively transferred into a 250-mL
beaker and was dissolved with 40 mL
distilled water.

The mixture was then filtered and a clear
filtrate was obtained. 45 mL of 10%
MgSO47H2O was added to the filtrate. Then,
150 mL of 2M NH3 was added slowly and the
mixture was stirred until a white precipitate
was formed. It was then allowed to stand for
15 minutes to complete precipitation.

The precipitate was transferred to the
pre-weighed filter paper and was washed
with two 5 mL portions of distilled water and
then with two 10mL portions of ethanol. The
filter paper was spread in a watch glass and
stored in the locker until the next lab period.
It was then heated in the oven for 1 hour and
was allowed to cool before weighing.

All data obtained were recorded.

RESULTS AND DISCUSSION

In this experiment, the main objective
was to determine the moisture and
phosphorus content of the fertilizer sample.
The first part of the experiment primarily
focused on the determination of the moisture
content of the fertilizer while the second part
was mainly about the phosphorus content
analysis.
Since all solids have a certain affinity
for water and may absorb moisture from the
laboratory air, the constant weighing process
was done in the two parts of the experiment
in order to prevent the moisture from the
surroundings from affecting the weight
obtained in all the weighing process
[2]
.
Table 1. Moisture Content Determination
Values

Mass of Water, g: 0.0384 0.0003
%Moisture: 1.23 0.01

The net weight of dried sample could
be obtained by subtracting the constant
weight of the empty crucible from the
constant weight of crucible with sample. In
order to determine the mass of water present
in the sample, the net weight of dried sample
was subtracted from sample weight. Also, by
using the formula:

ie
f e
e eigh
(2)

the percent moisture present could be
obtained. In the experiment, the calculated
percent moisture was 1.23%.

All fertilizers are more or less
hygroscopic, which means that they start
absorbing moisture at a specific humidity.
Some very hygroscopic fertilizers attract
moisture much more readily than others. If
the fertilizer had significant water uptake, the
quality of the fertilizer deteriorates.
[3]
Caking
and dust formation can easily occur.
[4]

Because of these said reasons, the
determination of fertilizer moisture content is
significant in order to assess the quality of the
product.

Other primary methods used for
moisture determination aside from oven
drying are spectroscopic, chemical, and
conductive analyses. Thermogravimetry and
combustion analysis is also widely used in
moisture determination.
[2]


In the experiment, weighing by
difference was used instead of direct
weighing because it gives more reliable and
accurate data. It is advantageous when
transferring hygroscopic compounds because
the vial used in transferring the sample is
exposed to the air less frequently
[5]
. Also, the
process eliminates or lessens the possible
loss due to incomplete transfer of sample
ince i den e he ineedie bjec
when transferring samples.

It is important to cool the crucibles
first before weighing so as to have
equilibrium with the environment. Samples
that are too hot will set up convection
currents and the apparent sample weight will
be incorrect. Warm samples are lighter while
cool samples are heavier
[5] [6]
.

Grinding the sample before oven drying
was necessary in order for the air trapped
inside the particles be released. Also, grinding
the sample provided a greater chance of
vaporizing the water in the tiny particles.

Weight readings are considered constant
when two consecutive weights are within
0.0003 g since the uncertainty of the
analytical balance is 0.0002-0.0003 g.
Having 0.0003 g as the highest value of the
margin of error means that the exact weight
of the sample lies within is 0.0003 g.

There are number of sources of error in
the experiment. These may include: touching
the crucible during the weighing process,
which may have added moisture to the
sample and increasing its weight; the spilling
of sample during weighing or transfer which
might have changed the recorded weight; and
not enough heating and cooling time which
may have the incomplete removal of moisture
from the sample.

In the second part of the experiment, the
phosphorus content of the fertilizer sample,
expressed in %P and %P2O5, where
determined through gravimetric analysis of
the precipitate formed which is magnesium
ammonium phosphate hexahydrate,
MgNH4PO46H2O, then became magnesium
ammonium phosphate, MgNH4PO4, due to
heating.

The first step in this analysis involved
the preparation of solution containing a
known weight of sample. The solution was
prepared through the addition of 10%
MgSO47H2O and 2 M NH3 to the oven-dried
fertilizer sample and was given by chemical
equation (1).

A series of filtration processes was
conducted in order to ensure high purity of
the white precipitate, MgNH4PO46H2O

The third step was isolating the
desired constituent. The precipitate was
weighed in the analytical balance. The last
step was computation of specific component
from the weight of precipitate. The
phosphorus component was computed from
the weight of precipitate through the use of
gravimetric factors.

After the preparation process, the
mixture was slowly added with ammonia
(NH3). The slow addition of NH3 made sure
that the co-precipitation of other compounds
such as Mg(OH)2 was prevented since the
formation of these other compounds will
lower the yield of the desired hexahydrate.
Also, the slow addition of NH3 with constant
stirring caused the precipitation to go faster
since it converted all ammonia into NH4
+
that
caused greater number of collisions.

The mixture then underwent a digestion
process after precipitation. Digestion is
important in gravimetric analysis since it
stimulates recrystallization of precipitates. In
digestion, weakly bound water will be
removed and lost in the precipitate resulting
into a denser mass and easy to filter
precipitate.
[5]


A 95% ethanol was then poured and was
used to wash the precipitate in order to make
it dry faster. Ethanol is volatile and attracts
water molecules so as it evaporates, the
water molecules are also carried away.

The addition of NH3 resulted to the
reaction with MgSO47H2O forming Mg
2
+ and
NH4
+
which were

necessary for precipitation.
If NH4Cl was used, the precipitate would not
have been visible and would have formed NH3
and Cl
-
instead. It would have also resulted to
an acidic solution since hydronium ions
would have been present making the
precipitate more unstable and soluble.

Table 2. Phosphorus Content Determination
Values

%P (wet basis): 10.977 0.002
%P (dry basis): 11.120 0.002
%P2O5 (wet basis): 25.155 0.005
%P2O5 (dry basis): 25.481 0.005

The value of the net weight was
obtained by subtracting the weight of the
filter paper from the weight of the filter paper
with precipitate. In the calculation of the
netweight and %P and %P2O5, the following
formula was used:

()
(

)
( )
(3)

()

)
( )
(4)


For the dry basis, the denominator
was just replaced with weight of dried sample
weight.

Possible sources of errors on
phosphorus determination include:
insufficient amount of digestion which may
cause incomplete collection of precipitate,
fast addition of NH3 or not stirring the
solution well, because it would not let NH3
convert into NH4
+
and would make
precipitation slow, and inefficient filtration
which will cause loss of precipitate and will
affect the phosphorus content computation.

CONCLUSION AND RECOMMENDATION

The first part of the experiment aimed
to determine the amount of moisture present
in the fertilizer sample. With the use of the
concept of constant weighing, it was found
out that the amount of water present in the
certain sample was 0.0384 g and a moisture
content of 1.23%. The results showed that the
sample has relatively low moisture content.
Having low moisture content is an indication
of a good quality fertilizer. If a fertilizer has
high moisture content, its effectivity and
quality will be lowered thus, affecting plant
growth.

The second part focused on the
determination of the phosphorus content of
the fertilizer sample. The precipitate,
MgNH4PO4, a product of the reactions of the
fertilizer sample, NH3, and MgSO47H2O, was
analyzed

by the use of gravimetric methods.
The phosphorus content was expressed in %P
and %P2O5 on both wet and dry bases. The
fertilizer contained 10.977%P on wet basis,
11.120%P on dry basis, 25.155%P2O5 on wet
basis, and 25.481%P2O5 on dry basis. The
high phosphorus content of the sample,
slightly more than 20.0% standard, shows
that it is of good quality.

The whole experiment is considered
to be successful since it produced and showed
the expected values and characteristics of the
commercial fertilizer sample having a low
moisture and high phosphorus content.
Having a phosphorus content slightly higher
than 20.0% is acceptable since its minimum
ve, bed n wh wien n he be, i
20.0%.

Thgh geney ccef, i cn
be denied h hee bbiiy h he
measured moisture and phosphorus content
of the sample is not accurate due to some
errors in the experiment. These errors may
include the insufficient time of cooling and
heating, the addition of moisture due to the
touching of crucibles, fast addition of NH3,
and the skipping of the digestion part which
may have resulted to the inefficient filtering
of the precipitate.


REFERENCES

[1] Capati, C.; Carpio, L.; Cuenco, F.; dela Isla,
B.; Erasquin, U. J.; Esguerra, M.; Ignacio, P.;
Lim, R.; Pacardo, D. K. Gravimetric
Determination of Moisture in Fertilizer
Samples. In Analytical Chemistry Laboratory
Manual: Quantitative Inorganic Analysis,
version 2007; Institute of Chemistry, College
of Science, University of the Philippines:
Quezon City, 2007 pp 19-20.

[2] Chapter XV: Gravimetric Methods. UMass
Amherst: Department of Civil and
Environmental Engineering Courses. [Online].
http://www.ecs.umass.edu/cee/reckhow/
courses/572/572bk15/572BK15.html
(accessed September 17, 2014).

[3] Physical Properties of Fertilizers. Crop
Nutrition|Yara.[Online].
http://www.yara.co.uk/crop-nutrition/safe-
handling-of-fertilizer/physical-properties-of-
fertilizers/ (accessed September 17, 2014)

[4] Faraji, H.; Crowe, T.; Besant, R.;
Sokhansanj S.; Wood, H. Prediction of
moisture content of potash fertilizer using
NIR spectroscopy. Journal [Online] 2004, 46,
3.45-3.48.
http://www.engr.usask.ca/societies/csae/pr
otectedpapers/c0301.pdf (accessed
September 17, 2014).

[5] Skoog, D.; West, D.; Holler, F.; Crouch S.
Fundamentals of Analytical Chemistry, 9th ed.;
Brooks/Cole: California, 2013.

[6] Harris D. Quantitative Chemical Analysis,
8th ed.; W.H. Freeman and Company: New
York, 2010.




























APPENDIX

A. Sample Calculations
Net weight of Dried Sample = Constant Wt. of Crucible + Sample - Constant Wt of Empty Crucible
= 35.4617 g 35.4917 = 2.9630 g

()

(


)

(


)

)

( )
(

)
( )

(


)


( )
(

)
()

(


)

( )
(

)
( )

( )
(

)
()

)



Data Sheet

Table 3. Constant Weighing of Crucible with Cover

Weighing 1, g: 32.4994 0.0002
Weighing 2, g: 32.4987 0.0002
Weighing 3, g:
Constant Weight, g
32.4988 0.0002
32.4987 0.0002


Table 4. Sample Size

Sample Weight, g: 3.0014 0.0002


Table 5. Constant Weighing of Crucible with Cover and Fertilizer Sample

Weighing 1, g: 35.4658 0.0002
Weighing 2, g: 35.4750 0.0002
Weighing 3, g:
Weighing 4, g
35.4617 0.0002
35.4648 0.0002
Constant Weight of Crucible + Sample, g: 35.4617 0.0002
Constant Weight of Empty Crucible, g: 32.4987 0.0002
Net Weight of Dried Sample, g: 2.9630 0.0003



Table 7. Sample Size / Weight of Filter Papers / Weight of Precipitate

Sample weight (as received), g: 3.0014 0.0002
Sample weight (dried), g: 2.9630 0.0002
Weight of filter paper, g: 1.4235 0.0002
Weight of air-dried filter paper with
precipitate, g:
2.8844 0.0002
Net weight of dried precipitate, g:

1.4609 0.0003




Solution Preparation

)(

)( )