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Potentiometric Determination of Phosphoric Acid in Unknown Sample

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Potentiometric Determination of Phosphoric Acid in

Unknown Sample

Jonniel Vince Cruz


College of Science, Pamantasan ng Lungsod ng Maynila
Received: 23 July 2014

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.

INTRODUCTION Because the slope reaches its


maximum value at the inflection point, the
Aside from a classical method of first derivative shows a spike at the
using indicators in locating a titration’s end equivalence point.
point, an alternative approach is to The second derivative of a titration
continuously monitor the titration’s progress curve may be more useful than the first
using a sensor whose signal is a function of derivative because the equivalence point
the analyte’s concentration. The result is a intersects the volume axis.
plot of the entire titration curve, which can The potentiometric titration is a
be used to locate the end point with a useful means of characterizing an acid. The
minimal error. change in pH is small until the end point
In this method, locating the end point where there is a sharp change. The strength
is to plot the titration curve’s first derivative, of an acid or base determines the sharpness
which gives the titration curve’s slope at of the change. It is not necessary to add the
each point along the x-axis. In a titrant dropwise as was required to obtain
conventional standpoint, the titration curve’s the exact equivalence point using a visual
slope changes as the volume approach, indicator.(Vaze, n.d.)
reach, and passes the equivalence point.

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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

6 2.95 6 0.04 17.5 0.18

6.5 0.14 18 7.74 18 0.04

7 3.09 7 0.05 18.5 0.22

7.5 0.19 19 7.96 19 0.07

8 3.28 8 0.07 19.5 0.29

8.5 0.26 20 8.25 20 0.38

9 3.54 9 0.39 20.5 0.67

9.5 0.65 21 8.92 21 0.87

10 4.19 10 1.22 21.5 1.54

10.5 1.87 22 10.46 22 -0.96

11 6.06 11 -1.31 22.5 0.58

11.5 0.56 23 11.04 23 -0.31

12 6.62 12 -0.31 23.5 0.27

12.5 0.25 24 11.31 24 -0.09

13 6.87 13 -0.05 24.5 0.18

13.5 0.2 25 11.49 25 -0.06

14 7.07 14 -0.03 25.5 0.12

14.5 0.17 26 11.61 26 -0.03

15 7.24 15 -0.03 26.5 0.09

15.5 0.14 27 11.7 27 -0.01

16 7.38 16 0.04 27.5 0.08

16.5 0.18 28 11.78 28 -0.02

8.88E- 28.5 0.06


17 7.56 17
16

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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

One method of finding the end point


is to plot the first or second derivative of the
titration curve. The slope of a titration curve
reaches its maximum value at the inflection
point. The first derivative of a titration
curve, therefore, shows a separate peak for
each end point. The first derivative is
approximated as ΔpH/ΔV, where ΔpH is the Figure 2. Graph of pH against volume of titrant
change in pH between successive additions
of titrant. (Table 1)The first number in the
third column, 0.5, is the average of the first
two volumes (0 and 1) in the first column.
The derivative ΔpH/ΔV is calculated
from the first two pH values and the first
two volumes (Table 1):

The coordinates (x = 0.5, y = 0.04) are one


point in the graph of the first derivative in
Figure 3. The second derivative is computed
from the first derivative. The first entry in
the fifth column of Table1 is 1.0, which is
Figure 3. Graph of ΔpH/ΔV against volume of
titrant
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Figure 3: At the second equivalence point,
the curve passed through the x-axis at
volume 21.4704 mL, indicating that it is the
volume at 2nd equivalence point. This
volume will serve as the equivalence volume
which reacted with phosphoric acid in a 2:1
ratio: 2 mol OH- ≡ 1 mol H3PO4.
After determining the equivalence
volume and calculating the Molarity, the
following table then summarizes the results:
Table 3. Summary of equivalence volume
Figure 4. Graph of Δ (ΔpH/ΔmL)/ΔmL against approximations
volume of titrant
Volume of sample (mL) 10.00 (±0.02)
By manually determining the volume Volume of NaOH used
at which the plotted curve reaches inflection 21.4704
(mL) at equivalence
point (in pH curve), maximum point (±0.0001)
point
(ΔpH/ΔV curve), and the x-intercepts, and Concentration of NaOH 0.0916
zooming in the Microsoft Excel’s calibration (M) (±0.0017)
lines, the following readings were obtained:
Concentration of
Table 2. Summary of equivalence volume Phosphoric Acid in 0.0983(±0.0018)
approximations Unknown
pH Curve True Value 0.1 M
st
1 Veq ~11 mL
nd
2 Veq ~22 mL Percentage Error 1.70 %
FIRST DERIVATIVE
1st Veq 10.50 mL Potentiometric (derivative) methods
2nd Veq 21.49875 mL are practically well-suited for locating end
SECOND DERIVATIVE points in multiprotic and multicimponent
1st Veq 10.4832 mL system, in which the use of separate visual
2nd Veq 21.4704 mL indicators for each end point is impractical.
(Harris, 2010) The precision with which the
From the given figures, the following
end point may be located also makes
observations were drawn:
derivative methods attractive for the analysis
Figure 1: The equivalence points are barely of samples with poorly defined normal
visible in the curve. The volume at the 2nd titrations curves. Though, potentiometric
equivalence point is approximately 22 mL endpoint determination is extremely
laborious and time-consuming since every
Figure 2: The equivalence points are visible,
showing greater accuracy. The last increment will be measured, and it requires
maximum point indicated that the volume at calibration for extreme pH ranges.
the last equivalence point is 21.49875 mL. Potentiometric titration required regular

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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.)

Most species require a pka difference


of 3.0 such that the buffer region at pka ±1.0 CONCLUSION
will not coincide with the endpoint. When
this happened, no abrupt change of pH will The phosphoric acid content of an
be observed as it is included in 10-90 % unknown sample was analyzed using
range for an effective constant pH. Also, the potentiometric titration; that is tracking
relative concentrations of titrant and analyte changes in the p-function of hydronium ions
do not differ logarithmically as each proton present in the solution. In the experiment, it
will not simultaneously be independent at all was found that the analyte contained
equilibria present; and less sharp endpoint 0.0983(±0.0018) M of phosphoric acid; as
will be achieved. compared to the true value of 0.1 M,
yielding a percentage error of 1.70 %. Thus,
Using the pH meter, it was found out potentiometric methods were proven to be
that the potentiometric determination of useful in locating end points in multiprotic
phosphoric acid proved to be a good and multicomponent systems, in which the
titrimetric method for an unknown sample. use of separate visual indicators for each end
After calculating the values, the point is impractical.
experimental value of 0.0983(±0.0018)
against a true value 0.1 M yielded an
acceptable percentage error of 1.70 %, REFERENCES
largely due to activity effects, changing the
effective concentration of the acid. Since pH 1. Harris, Daniel C. "Acid Base
is dependent to the matrix of the analyte, Titrations." Quantitative Chemical
intermolecular forces could affect the Analysis. New York: W.H. Freeman,
thermodynamic behavior of the analyte; 1999. N. pag. Web.
which then causes an error in the 2. Skoog, Douglas A., Donald M. West,
experiment. Errors in disposing the expected and F. James. Holler. "Principles of
volume of the titrant, and personal biases Neutralization Titrations."
during reading the pH meter might also Fundamentals of Analytical
affected the analysis. To ensure minimal Chemistry. Fort Worth: Saunders
personal and random errors, it is College Pub., 2013. N. pag. Web.
recommended to use an autotitrator. 3. Splawn, Bryan. Potentiometric Analysis
Derivative methods work well only of Acid in Coke. none: Independent
if sufficient data were collected during the Publisher, 0. Web.
rapid increase in pH near the equivalence 4. Vaze. "Determining the Phosphoric
point. Because the pH changes so rapidly Acid Content in Soft Drinks."
near the equivalence point—a change of Sample_Labs. N.p., n.d. Web. 9 Apr.
several pH units with the addition of several 2014
drops of titrant is not unusual—a manual
titration with large increments does not
provide enough data for a useful derivative

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