Potentiometric Determination of Phosphoric Acid in Unknown Sample
Potentiometric Determination of Phosphoric Acid in Unknown Sample
Potentiometric Determination of Phosphoric Acid in Unknown Sample
Unknown Sample
ABSTRACT
This experiment aimed at analyzing the phosphoric acid content of an unknown sample
using potentiometric titration. During titration, the data was obtained by monitoring the change
in pH instead of using visual indicators to determine the endpoint, as it provides a more accurate
location of the equivalence point in a titration. Graphical location and mathematical operations
involving derivatives to locate the curves’ maximum slope were used to determine the endpoint
of titration. Using the pH meter, it was found out that the unknown sample contained
0.0983(±0.0018) M phosphoric acid, as compared to the true value of 0.1 M; yielding a
percentage error of 1.70 %. Based on the results, potentiometric methods were proven to be
useful in locating end points in multiprotic and multicomponent systems, in which the use of
separate visual indicators for each end point is impractical. To ensure minimal personal and
random errors, using an autotitrator is recommended.
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The potential is internally measured reading reached 12. The approximate
across the analyte, typically an electrolyte equivalence point was determined by noting
solution. Two electrodes are used, an the volume at which a large change of pH
indicator electrode (the glass electrode and occurred.
metal ion indicator electrode) and a
reference electrode.
In this experiment, potentiometric RESULTS AND DISCUSSION
titration is used to analyze the phosphoric
acid content of a given brand of unkown Analysis of Sample
solution. The concept of the titration curve is
applied in determining the end point of an In the experiment, the potentiometric
acid-base titration. titration was applied to determine the
phosphoric acid content an unknown
sample. From the excess sample, 10.00 mL
METHODOLOGY aliquot was obtained. If the sample was
included in a multicomponent solution,
Standardization of NaOH solution boling the sample was necessary due to the
large amount of dissolved carbon dioxide
A previously prepared NaOH and small amounts of carbonic acid. Boiling
solution was restandardized by titrating it effectively destroys this buffer by
against a primary standard. A mass range of eliminating the carbonic acid (Skoog et al.,
0.1000-0.2000 gram KHP, determined using 2013):
analytical balance was dissolved in 20 mL H2CO3 (aq) CO2(g) + H2O(l)
distilled water. The solution was titrated
with the prepared NaOH solution to the end Carbon dioxide reacts rapidly with
point after addition of 3 drops of hydroxides, which then changes the
phenolphthalein indicator. expected stoichiometry when two moles of
acid react with every mole of carbonate
Analysis of Sample base. This would cause the curve to diverge
from the normal since phosphoric acid
Ten milliliters (10 mL) of the sample titrated with two bases will form a reaction
was transferred into a 250 mL beaker, and which required complex calculation to
was diluted by adding forty milliliters (40 negate the buffering effects in the solution.
mL) of distilled water. The set up for The solution then would become less acidic
potentiometric titration was arranged as due to the carbon dioxide which may
shown in Figure 1. The potentiometric interfere with the titration.
titration was done by adding increments of The titration was performed by
1.00 mL of the standard NaOH solution to adding 1.00 mL increments of 0.0916
the sample, (±0.0017) M standardized NaOH solutions
recording the (Table 1). Instead of adding large amounts
pH for every of sodium hydroxide solution, titrating with
addition. smaller, uniform increments tends to
Addition of the equilibrate the reacting vessel, stabilizing
NaOH solution the mixture faster than using bulk amounts.
was stopped Additions of titrant were stopped as pH
when the pH reading reaches 12.
Figure 1. Setup for Potentiometric titration
(regressioninbiologicalchemistry.weebly.com)
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At pH 10.5-11.00 the glass electrode pH meter will not be constant, thereby
begins to detect the potential from other increasing the error in determining the
species, as most acidic protons from endpoint of the analyte.
phosphoric acid had already reacted. This
phenomenon that causes the reading to After all the pH values were
appear at pH lower than it really is, is called recorded, equivalence point was determined
alkaline error. Its occurrences made it by graphical means. Using Microsoft Excel,
advisable not to carry the titration beyond the following curves were required:
pH= 10.5; which caused the experimenters
not to observe the third equivalence point of (1) pH against volume of the titrant
phosphoric acid: (Splawn, n.d.) (2) ΔpH/ΔV against volume of the titrant
(3)Δ2pH/ΔV2 against volume of the titrant
HPO42- + OH- PO43- + H2O
(cannot be detected accurately using pH From the following curves, the data
electrode) recorded should first be calculated using
derivatives to find the maxima and inflection
Glass surfaces become responsive point of the curve:
not only to hydrogen ions but also alkali
metal ions. As a result, measured pH values Table 1. Data in titration of phosphoric acid in
would be lower than theoretical. an unknown sample
The third equivalence point for
phosphoric acid in the experiment will not Δ(ΔpH
give accurate results mathematically if 5.00 mL ΔpH/
pH mL mL /ΔmL)/
mL increments are used – the changes NaOH ΔmL
ΔmL
increase exponentially causing multiple
(greater than the expected value) inflection 0 2.52
points for the given titration curve. When
the solution approaches equivalence point, 0.5 0.04
very abrupt change is evident in the plotted
curve even for very small increments of 1 2.56 1 0.01
titrant; thus, a large amount of titrant will
likely give a linearized – and not a sigmoid 1.5 0.05
curve. The curve will be very different from
2 2.61 2 0.03
the theoretical, and a different extrema
(maxima and minima) values would be 2.5 0.08
calculated.
3 2.69 3 -0.01
In the experiment, constant stirring
(use of magnetic stirrer) was necessary as it 3.5 0.07
ensured uniform concentration of all
reagents (analyte and titrant) such that it 4 2.76 4 0.02
would react more completely. Also, it
provided the mechanical energy necessary to 4.5 0.09
make a consistent pH reading for a given
volume. If continuous stirring was not 5 2.85 5 0.01
employed, fluctuations of reading would be
5.5 0.1
evident since the potential measured by the
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Table 1. Data in titration of phosphoric acid in an unknown sample, contd.
mL Δ(ΔpH Δ(ΔpH
ΔpH/ mL ΔpH/
NaOH pH mL mL /ΔmL)/ pH mL mL /ΔmL)/
ΔmL NaOH ΔmL
ΔmL ΔmL
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Table 1. Data in titration of phosphoric acid
in an unknown sample, contd. the average of 0.5 and 1.5. The second
derivative is
Δ(ΔpH
mL ΔpH/
pH mL mL /ΔmL)/
NaOH ΔmL
ΔmL
29 11.84 29 0
The coordinates (x= 1.0, y= 0.01) are
29.5 0.06
plotted in the second derivative graph in
30 11.9 30 -0.01 Figure 4. Phosphoric acid content could then
be identified using the interpolated volume
30.5 0.05 at the equivalence point of second derivative
31 11.95 31 -0.01 curve. The following curves are generated
from the points calculated from Table 1:
31.5 0.04
32 11.99 32 0.01
32.5 0.05
33 12.04
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maintenance as it is extremely sensitive to titration curve. A manual titration does
external factors (pressure, temperature, contain an abundance of data during the
humidity, and lighting for chemically more gently rising portions of the titration
curve before and after the equivalence point.
sensitive or photosensitive reagents.)
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