Experiment #4: Conductometry

Conductometric measurement of solubility product;

Conductometric titration of acid mixture with strong base;
Conductometric and Fluorometric Analysis of Acetyl Salicylic Acid in Aspirin Tablets

4.1 Conductometry
Electrical conductivity occurs in different materials, by the flow of electrons (such as in metals or
semiconductors) or by movement of other charged species (such as electrolytes). Conductivity of
electrons is measured by applying a potential between two electrodes immersed in the electrolyte
solution. An electric field is generated between the two electrodes, which causes the ions to migrate:
negative ions migrate towards the positive electrode and positive ions migrate towards the negative
electrode. During the application of potential, a charging process occurs in the proximity of the electrodes.
Positive charges accumulate close to the negative electrode, and negative charges accumulate close to
the positive electrode. This charging process stops after a very short duration of time (fractions of a
second), and it results in a potential difference between the metal electrode and the solution in its
proximity (up to a distance of micrometers). This potential eventually equals the applied potential, and
the field generated between the electrodes cancels out, following which the charges stop migrating.
Therefore, it is impossible to measure the conductivity of a solution with a regular Ohm-meter, which
applies a straight potential (or current). A conductometer is an instrument that performs the
measurement with a cyclic potential, in which the cycle duration is very short, compared to the time
required for charging, which results in measurement inaccuracies. The field generated changes its
direction according to the applied potential. As a result, the migration of ions becomes cyclic, and the
measured current is also cyclic. Electrically, there is no difficulty measuring a cyclic current, which is
proportional to the conductivity, which is dependent on the concentration.

Raising the temperature of electrolytic solutions improves the mobility of the charged species, and
therefore improves the conductivity. On the other hand, conductivity in metals decreases with higher
temperatures. A special type of conductivity exists in gas phase (“plasma”), in which both ions and
electrons conduct electricity when a potential is applied between two electrodes.

For electrolytic solutions of ions, the magnitude of the current is dependent on the number and type of
ions, their mobility, the solvent, and the potential applied. The number of ions depends on the
concentration, but for weak electrolytes it is also dependent on the degree of ionization and the
temperature.

Definitions and units

According to Ohm’s law, the current I (Ampere) that flows in the conductor is directly proportional to the
potential applied, E (Volt) and is proportional to the reciprocal to the resistance R (ohm, Ω) of the
conductor. The famous equation:

1
 E E
1. i  , R
R i
For a conductor with a uniform structure and cross-section, the resistance is proportional to the length, l,
and proportional to the reciprocal of the area, A. The standard unit of resistance in metal and electrolytic
conductors is termed specific resistance ρ (Ohm x cm), and it is the resistance of a conductor with a length
of 1 cm and a cross-section of area equal to 1 cm2. The resistance of a conductor of length l and area A
will be:

l
2. R   
A
The reciprocal of the resistance is the conductivity, S=1/R (Siemens) and the specific conductivity κ:
1 A
3.  S  
R l

Equivalent conductivity
If there is no mutual effect on the ions, the specific conductivity of electrolytic solutions depends linearly
on the concentration of the ionic species in the solution, and on the properties of each ion in the solution.
It is useful, therefore, to define electrolytes in such a way that takes concentration into consideration. The
properties of each electrolyte must be expressed through a parameter that is independent of the
concentration, and can be measured for each electrolyte. This factor is known as equivalent conductivity,
and is defined as the conductivity of a hypothetical solution containing 1 gram/equivalent of solute
between two parallel electrodes placed at a distance of 1 cm from each other, each with an area of 1 cm2.
The weight of the gram/equivalent is the atomic or molecular weight of the ion, divided by the ion’s
charge. Therefore, the number of gram equivalents is the number of moles multiplied by the charge, and
the normality is the molarity multiplied by the charge. A solution of 1 N concentration requires 1000 cm3,
and according to equation 3, the equivalent conductivity Λ is defined as:

1000
4.    S  cm2  eq -1
N
The specific conductivity κ increases as the concentration increases, but the equivalent conductivity
remains constant, since the concentration appears in the denominator (equation 4). The ratio, therefore,
remains constant.

However, with the increase in concentration, a mutual effect of the ions is formed. It is due to their electric
charge, since each electrolyte is comprised of at least two different ions, with opposite charges.

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This effect is demonstrated in Table 1.

Normality 18 °C 20 °C 25 °C
1.000 0.09822 0.1021 0.1118
0.1000 0.01119 0.01167 0.01288
0.01000 0.001225 0.001278 0.001413
0.001000 0.0001271 0.0001326 0.0001469

The conductivity of an electrolyte solution is equal to the sum of conductivities of all ions in the solution.
For one dissolved salt, the equivalent conductivity can be expressed as:

5.     
where :   the equivalent conductivity of the cation
  the equivalent conductivity of the anion

For mixtures, Λ will be equal to the sum of all λ+ and all λ- of the individual ions comprising the solutions.
The equivalent conductivity of salts or ions increases as the concentration decreases. This phenomenon
is directly related to the inter-ion forces that operate in solution. For example, in the proximity of a given
cation there will be more anions, compared to the amount predicted from random distribution. This “ionic
atmosphere” has two effects: electrophoretic and time decay, both of which tend to reduce the mobility
of the ion. In the first case, the solvent molecules within the ionic atmosphere migrate in the opposite
direction from that of the central ion. In the second case, the ionic atmosphere moves more slowly than
the central ion, and causes charge separation (a detaining electrostatic force) on the central ion. As the
solutions become more dilute, the ionic atmosphere becomes weaker, and as a result, the two effects
(electrophoretic and time decay) also become weaker, proportional to the square-root of the solution’s
ionic strength. At infinite dilution, there are no additional effects governing the mobility of the ions, except
for changes in the solvent and temperature, and the equivalent conductivity reaches a maximal value.
Equation 5 can be written as:

6.  0  0  0
where :  0  the equivalent conductivity of the electrolyte at infinite dilution
0  the limiting equivalent conductivity of the cation at infinite dilution
0  the limiting equivalent conductivity of the anion at infinite dilution

Onsager demonstrated that it is possible to connect Λ (at infinite dilutions) and Λ0 by:

7.  = 0  ( A  BA0 ) c
where : A  a correcting factor for the electrophoretic effect
B  a correcting factor for the time decay effect

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Table 2 displays the equivalent conductivities at infinite dilution for various ions.

Anion 0 - Cation 0 +
OH- 198.6 H+ 349.8
F- 55.4 Li+ 38.6
Cl- 76.4 Na+ 50.1
Br- 78.1 K+ 73.5
I- 76.8 Ag+ 61.9
NO3- 71.5 NH4+ 73.3
ClO4- 67.4 Hg2+ 53
CH3COO- 40.9 Mg2+ 53.1
SO42- 80.0 Ca2+ 59.5
CO32- 69.3 Ba2+ 63.6
Cu2+ 53.6
Zn2+ 52.8
La3+ 69.7
Ce3+ 69.8

Using Table 2, it is possible to calculate the conductivity that will be obtained in different solutions:

From equations 3, 4 and 5 we obtain:

A (λ   λ  )CiZi
8. S  (CiZi  Ni )
l 1000
Or in case of a mixture:

A λiCiZi
9. S 
l
 1000
It is also possible to see that the equivalent conductivity is in fact an identifying factor for the type of ion,
since this value does not change significantly with the concentration (Table 1, after dividing the specific
conductivity by the concentration).

The Cell Constant

As stated above, the measurement must be performed in a well-defined cell. In practice, it is not
necessary to design a cell with two platinum electrodes of exactly 1 cm2 area and at a distance of 1 cm
exactly between them, in order to measure specific or equivalent conductivity. It is more plausible to
design a cell and define a cell constant, using solutions of known specific conductivity. Usually, KCl
solutions are used, since their specific conductivities have been measured at high accuracy. The data in
Table 1 can be used to calibrate the measurement cell.

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The cell constant, K, is expressed in terms of the resistance, R, and the κ of the solution:

10. K   R cm1
Therefore, if K=1, the resistance measured is numerically equal to the reciprocal of the specific
conductivity of the analyzed solution. Once K is determined for a cell, it is possible to extract the values of
A or κ from the resistance measurements, using equations 4 or 10, respectively.

Conductometric titrations and other applications

One of the common usages of conductometry is for quantitative titrations for systems in which the
conductivity of the solution changes in such a way that enables (before and after the end-point) drawing
two intersecting lines to indicate the end point. The shape of the titration curve depends on the sample,
the titrant, and the reaction taking place. To achieve maximal accuracy in the titration, it is often necessary
to correct for the resistance due to dilution by the titrant. To minimize this correction, the titrant must be
10 times, preferably 100 times, more concentrated than the solute. Dilution corrections for the titrant are
performed by:

Vv
11. Sc Sm
V
where : Sm  measured conductivity
Sc  corrected conductivity
V  original volume of the solution
v  volume of titrant added before reading Sm

Usually, 4-6 data points are collected before the end-point, and an additional 4-6 points after it.

Acid-Base Titrations
Strong acids and bases
Because of the high mobility of H+ and OH- ions, the sharpest and most accurate end points are obtained
when a strong acid is titrated with a strong base, and vice versa. From Table 2, we can observe that the
equivalent conductivity (or mobility) of H+ and OH- is 5 and 3 times higher than the rest of the ions,
respectively.

A typical example is the titration of 100 mL 0.001 N HCl solution with 0.1 N NaOH:

H 
 Cl     Na   OH     Na   Cl    H 2O

Figure 3 shows a titration curve: at the beginning, the conductivity decreases rapidly, due to gradual
exchange of H+ ions with sodium. Then, after the end point, it increases rapidly when an excess of OH-
ions is added. The broken line represents the contribution of the NaCl formed by the neutralization
reaction salt to the conductivity. This line is significant in the titration of weak or very weak acids and

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bases – the conductivity usually follows this line up to the end point. If there are salts in the solution, the
curve in the figure continues upward and the relative change (measured by the conductometer)
decreases. When the concentrations of the salts are very high, the relatively small changes in the
conductivity create inaccuracies, and a potentiometric titration will provide better results.

Weak acids and bases.

In the titration of weak acids and bases, the end point is not as sharp as in the case of strong acids and
bases.

During the titration of a weak acid, Figure 4, the law of mass activities in in effect. In the case of acetic
acid titrated with NaOH, the shared ion OAc- causes a decrease in the concentration of the H+ ion, beyond
the stoichiometric neutralization. Since the increase in conductivity as a result of the formation of Na+ and
OAc- is smaller than the decrease as a result of loss of H+, then the total conductivity decreases in the
initial stages of the titration. At a certain point, depending on the concentration of the acid being titrated
and its pKa, the concentration of the H+ ions is practically negligible and the conductivity of Na+ and the
acid’s anions follow the salt line in the figure.

Figure 1. Titration curves of the neutralization of 0.001 N HCl with (a) 0.1 N NaOH; (b) 0.1 N NH4OH.

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However, as a result of the hydrolysis of sodium acetate, the line becomes curved close to the end point.
Figure 5 shows some titration curves of acetic acid with NaOH and with the weak base NH4OH at a
concentration of 0.001 N. The figure shows the effect of the ionization constant of the acid at a
concentration of 0.1 N on the shape of the titration curve.

Figure 2. A) Titration of acetic acid in various concentrations: a) 0.01 N; b) 0.001 N; c) 0.0001 N (titration with NaOH); d) 0.001 N
(titration with KOH or NH4OH). B) Titration of a number of weak acids with NaOH.

Curve c in the figure indicates that the very dilute solution of acetic acid (concentration 0.0001 N)
dissociates in such a way that no part of the line is straight, like in curve a, in order to calculate the end
point. Even for solutions at a concentration of 0.0001 N (curve b), only 20% of the neutralization reaction
is linear, and it is necessary to be extremely careful in determining the end point.

When the base is NH4OH (curve d), the end point is observed more sharply. In this unique circumstance,
the titration up to the end point will proceed as though the titrant is a strong base. However, after the
end point, because of the shared ion effect (NH4+) the conductivity remains constant, since NH4OH
remains mostly in its neutral form. In addition, since the conductivity of NH4+ (λ0=73) is higher than the
conductivity of Na+ (λ0=50), the conductivity before the end point rises more rapidly, and hence increases
the angle at the end point.

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Figure 5B indicates that a relatively strong acid (Ka=10-1) at a concentration of 0.1 N can be titrated, if the
number of data points collected is between 50 and 100. A V-shaped curve is obtained with a small degree
of curvature. The curve distorts rapidly when weaker acids are titrated. For example, for an acid with
pKa=2, there is no linear part on the plot, to enable determination of the end point.

Diluting relatively strong acids will usually result in better titration curves. For example, a solution of an
acid with pKa=2 at a concentration of 0.1 N will dissociate into ions (62%, compared to 27%) if it is diluted
by a factor of 10. As a result, the titration curve will appear more similar to that of an acid with pKa=1 at
a concentration of 0.1 N. Greater dilution will produce better V-shaped curves, at least up to the
equivalence point.

In general, it is possible to titrate relatively strong acids and bases, if their concentration is approximately
100 times smaller than their ionization constant. Alternatively, they can be titrated as weak acids, when
their concentration is at least 150 times larger than their ionization constant. For example, the final 25%
of the salt line will be measured for an acid with pKa=3 if its concentration is at least 0.15 N.

A method for obtaining a clear end point when a certain titration provides ill-defined curves is to titrate
equal aliquots of the weak acid with equal concentrations of KOH and NH4OH. The curves obtained before
the end point should be equal, but after the end point they will split along the strong and weak base lines.
It is important to note that in this technique the cations of the two bases have identical conductivities
(NH4+, =73; K+, =74). If the strong base is NaOH (Figure 5), an incorrect end point will be determined,
as seen from the comparison of the three base curves in the figure.

When no linear portion can be identified before the end point, it is possible to add alcohol or another
organic compound that dissolves in water. This will serve to reduce the dissociation of the acid, so that it
will behave more like a very weak acid. This is sometimes the easiest way of titrating weak acids. If this
technique fails, potentiometric methods should be considered.

Mixtures of weak and strong acids

When a mixture containing both a weak and a strong acid is titrated, the conductometry method will
usually be preferred above other methods, such as potentiometry. Figure 6 shows the changes in relative
conductivity that occur when a mixture of HCl and acetic acid is titrated with a) NaOH and b) NH4OH.

8
Figure 3. Titration of a mixture containing a weak and a strong acid with a) NaOH; b) NH 4OH.

When a mixture of a weak and a strong acid is titrated, a strong base must be used. Using a weak base
will lead to large hydrolysis effects and it will be impossible to identify the end point of the weak acid from
the plot. However, the first end point will give the concentration of the strong acid.

Salts of weak acids and bases

It is possible to titrate salts of weak acids with a strong acid, since they are themselves Bronsted bases,
meaning proton acceptors. An example of this is the titration of sodium acetate with HCl:

H   Cl   Na  OAc  Na  Cl   HOAc

When sodium acetate is titrated, the acetate ion is replaced with a chloride ion. Since the chloride ion has
a higher equivalent conductivity than the acetate, there is an increase in the conductivity up to the end
point. After the end point, an excess of HCl causes a sharp rise. These titrations are useful only when the
ionization constant of the resulting acid or base is divided by the salt concentration, and the value
obtained is smaller than 5x10-3. If a diprotic acid is formed, both ionization constants must differ by 10-5
(5 orders of magnitude) to show two distinct end points. An example of this is the Na2S salt. Figure 7 shows
two typical titration curves. These types of titrations are useful for salts such as oxalates, phosphates,
benzoates, etc.

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Figure 4. Replacement reaction of a) Na2S with HCl; b) NH4Cl with NaOH

4.1.1. Conductometric measurement of the solubility of a relatively insoluble compound: silver

acetate

Goal
To determine the solubility of silver acetate with the conductometric method.
By measuring the cell factor and the equivalent conductivity of silver nitrate, silver acetate and sodium
acetate solutions, it is possible to determine the solubility.

Literature
1. Reilley, C. N., High Frequency Methods, chap. 15 in “New Instrumental Methods in
Electrochemistry”, P. Delahay (ed.), Interscience, New York, 1954, p.319-345

2. Loveland, J. W. in “Treasite on Analytical Chemistry”, Kolthoff, I. M., Elving, P. J., Sandell, E. B., (eds.),
part I, vol. 4, Interscience, New York, 1963, chapter 51, p.2569-2629

Equipment
 Conductometer
 5, 10, 25, 50 mL pipettes.
 250, 800 mL beakers.
 Magnetic stirrer.

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Chemicals
 0.100 N AgNO3 standard, 110 mL
 0.100 N NaOAc standard, 110 mL
 0.100 N NaNO3 standard, 110 mL
 Concentrated AgOAc at 25 °C
 0.01 N KCl standard, 0.7459 g/L.

Background
The cell constant can be determined by measuring the conductivity of the standard KCl solution and
finding the specific conductivity in the literature. The cell constant is given by:

l  (table)
Cell constant  
A S (measured)

The equivalent conductivity of silver acetate can be found from the measurement of the conductivity of
the three solutions (silver nitrate, sodium nitrate, and sodium acetate), since:

1.   AgOAc     AgNO3     NaOAc  –   NaNO3 

From the plot of equivalent conductivity multiplied by normality as a function of normality, it is possible
to find the normality of the saturated silver acetate solution.

By plotting the equivalent conductivity of each salt against the square-root of the normality and
extrapolating to zero, it is possible to find the equivalent conductivity at infinite dilution. Such a plot will
give a straight line, according to:

2.    0  B N

The straight lines can be represented by the following equations:

3.  ( AgNO3 )   0 ( AgNO3 )  a N
4.  ( NaOAc )   0 ( NaOAc )  b N
5.  ( NaNO3 )   0 ( NaNO3 )  c N

N can be determined by solving the following equation:

l S
6. 1000   0 ( AgNO 3)   0 ( NaOAc)   0 ( NaNO 3)  ( a  b  c) N
AN
where : S  the measured conductivity of the solver acetate solution of normality N

This equation may also be solved graphically (plotting each of the sides of the equation as a function of N,
and finding the point/s of intersect between the plots), or by iteration; consult your instructor.

11
The normality calculated with this equation can be compared to the one obtained graphically.

Electrodes
For accurate conductivity measurement, platinized platinum electrodes are used, for which the
polarization effect that occurs when current is passed through the electrodes is reduced. In
conductometric titrations, where the end point must be determined precisely, but the exact absolute
value of the conductivity is less important, it is possible to use other electrodes (shiny platinum, tungsten,
etc.).

Experimental Procedure

During the whole experiment, use doubly deionized water (DDW)

Measure the conductivity of the 0.01 N KCl standard solution.

Accurately transfer 500.00 mL DDW (from a volumetric flask) into a clean 800 mL beaker and measure the
conductivity. Using a pipette, add 5.00 mL 0.100 N silver nitrate, stir well, and measure the conductivity
again. Continue adding the following aliquots of silver nitrate: 5, 5, 10, 25, 25, 25 mL (for a total added
volume of 100 mL). After each addition, stir the solution well and measure the conductivity.

Repeat the measurements as above, this time using the 0.100 N sodium nitrate solution. Then, repeat
again, using the 0.100 N sodium acetate solution.

Accurately dilute a saturated silver acetate solution by a factor of 5 (in 25 volumetric flask), and measure
the conductivity of the diluted solution.

Clean the cell well and store in DDW.

Results analysis
1. Calculate the cell constant using the literature value for the specific conductivity of KCl.
2. Calculate the normality (molarity multiplied by electric charge, Z) and the square-root of the normality
for each dilution of the solution (do this for one solution only, since the values will be identical for all
solutions of the same dilution, since their initial concentration is 0.1 N).
3. Calculate the equivalent conductivity for each salt. For each normality, calculate the equivalent
conductivity for silver acetate, using equation 1. Correct for the conductivity of water, by subtracting
this value from all of the salt conductivity results. Multiply each value of equivalent conductivity for
silver acetate by the normality (ΛN=κ).
4. Draw a plot of κ versus the normality. Read the normality for the saturated solution of silver acetate
from the plot, after multiplying Λ by N to obtain κ.
5. Plot the equivalent conductivity against the square-root of the normality for each of the salts, on the
same grid. Continue each line by extrapolation to zero (infinite dilution), in order to find Λ0 for each
salt. Compare your results with the literature values (Table 2).discuss each discrepancy.

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6. Use equations 3, 4, and 5 to solve a, b, and c. Calculate the normality of the silver acetate solution
from equation 6. Compare to the value obtained from the plot of κ versus the normality.
7. Compare the concentration of the saturated silver acetate solution calculated with two methods
(steps 4, 6).
8. Calculate the solubility product of silver acetate, and compare to literature values (note the source).

Questions
1. What are the main causes for inaccuracies and mistakes in the experiment?
2. Are the Λ0 values found experimentally in agreement with those reported in the literature (displayed
in the table)?

4.1.2 Conductometric titration of acid mixture with strong base

It is convenient to titrate mixtures of acids, using the conductometric method to determine the end point.
The method is especially useful when simple photometric and potentiometric methods do not provide
satisfactory results. In these cases, as long as one of the acids is strong, and the pKa values differ by at
least 5 units, then the part of the conductometric titration plot stemming from each of the components
will be well-defined.

In this experiment, we will titrate a mixture of CH3COOH, HCl, and NH4Cl (Bronsted acid) with NaOH.

Chemicals
 10mM KCl solution (for calibrating the conductometric cell)
 1 M NaOH standard solution
 0.1 M HCl
 0.25 M CH3COOH
 0.25 M NH4Cl
 Mixture of unknown composition (containing CH3COOH, HCl, NH4Cl)

Titration Equipment
The titration is performed by continuous addition of the titrant. A viton or tygon tube (internal diameter
1 mm) is recommended for use with the peristaltic pump.

The data will be transferred to the computer to monitor the data and analyze them.

Experimental Procedure
1. Determine the flow rate of the peristaltic pump: use a stop-watch to measure the duration of time
needed to fill a volumetric flask of 1.00 mL with the titrant, 1 M NaOH.

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2. For a qualitative titration, use a measuring tube to transfer the following into a 25 mL beaker:
5 mL 0.1 M HCl, 5 mL 0.25 M CH3COOH, 5 mL 0.25 M NH4Cl, and 10 mL distilled water.

3. Place the beaker on a magnetic stirrer, insert a magnetic stirring bar and immerse the conductivity
cell into the beaker, until it is fully covered. Adjust the speed of the stirrer to prevent formation of
bubbles. Titrate with NaOH at a rate of 0.8-1.0 mL/min. Operate the pump and data collection
program simultaneously (see previous section, “titration equipment”. Save your data by clicking on
write to file. Continue to titrate until you have 50% excess of titrant. Stop the pump and the data
collection.

At the end of data collection, find the times corresponding to the three titration end points. Print
the plot. In addition, accurately determine the end points from the data you have saved.

4. Clean the electrodes and the beaker. Use a pipette to transfer 10.0 mL of the unknown composition
mixture and 15 mL distilled water to a beaker and titrate in the same manner. (To obtain the data in
a new graph, exit the program by clicking exit; re-enter the program; change the parameters as
explained in the section titled “titration equipment”).

At the end of data collection, find the times corresponding to the three titration end points. Print
the plot. In addition, accurately determine the end points from the data you have saved.

5. Repeat the titration a second time.

At the end of data collection, find the times corresponding to the three titration end points. Print
the plot. In addition, accurately determine the end points from the data you have saved.

6. At the end of the experiment, clean the beaker, cell, and pump tools with DDW.

Results Analysis
Determine the end point of the analysis. Calculate the concentration of each component in the mixture
(in g/100 mL and mole/L units). Explain the shape of the titration curve, and compare it to a potentiometric
titration curve.

Questions
1. When is a conductometric titration preferable to different methods, such as potentiometric?
2. For which of the salts of weak acids or bases is it possible to use conductometric titration? How many
end points can be observed when the salts of multi-protic acids are titrated?
3. How can you explain the fact that it is necessary to use a strong base when titrating a mixture
containing a strong acid and a weak acid?
4. Is it possible to conductometrically titrate a mixture of CH3COOH, HCl and HNO3, and to accurately
determine the concentration of each of the components? Indicate which solvents and titrant must be
used for a successful titration.

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4.1.2 Conductometric Analysis of Acetyl Salicylic Acid in Aspirin Tablets
Experiment Procedure

Sample preparation
1. Obtain an aspirin tablet. Write down the name of the manufacturer and the amount of acetyl salicylic
acid reported by the manufacturer.
2. Prepare a beaker with 100 mL DDW and place it on a heating plate. Heat the water until just before
the boiling point. In the meantime:
3. Using a mortar and pestle, crush the tablet into a thin powder.
4. Position a glass funnel above a 100 mL volumetric flask.
5. Fold a #1 filter paper and place it in the funnel.
6. Transfer the powder quantitatively into a 100 mL glass. Add warm water, stir with a glass rod, and
then pass the mixture through the filter paper in the funnel. Continue to wash the beaker and transfer
the contents through the same funnel.
7. Slowly pour the warm water through the funnel, into the volumetric flask. The acetyl salicylic acid in
the powder will dissolve in the warm water and flow into the volumetric flask. Some of the binding
materials may not dissolve, and will remain on the filter paper.
8. Continue washing the powder with warm water up to a total volume of approximately half of the
flask.
9. After the contents of the flask have cooled to room temperature, add DDW up to the final volume of
100 mL. This sample will be used for the Conductometric Analysis.
10. For the Fluorometric Analysis, dilute the sample x100 in a 100 mL volumetric flask.

Titration Equipment
The titration is performed with the same equipment as the previous titration.

Experimental Procedure
1. Determine the flow rate of the peristaltic pump: use a stop-watch to measure the duration of time
needed to fill a volumetric flask of 1.00 mL with the titrant, 0.1 M NaOH.
2. Use a 25 mL pipette to transfer 25 mL of the aspirin solution (step 9 from the previous part) into a
25 mL beaker.
3. Place the beaker on a magnetic stirrer, insert a magnetic stirring bar and immerse the conductivity
cell into the beaker, until it is fully covered. Adjust the speed of the stirrer to prevent formation of
bubbles. Titrate with 0.1 M NaOH at a rate of 0.8-1.0 mL/min. Operate the pump and data collection
program simultaneously (see previous section, “titration equipment”. Save your data by clicking on
write to file. Continue to titrate until you have 50% excess of titrant. Stop the pump and the data
collection.
4. At the end of data collection, find the time corresponding to the end point. Print the plot. In addition,
accurately determine the end point from the data you have saved.
5. Clean the electrodes and the beaker, and repeat the titration two more times.
6. At the end of the experiment, clean the beaker, cell, and pump tools with DDW.

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Results Analysis
Determine the end point of the analysis. Calculate the amount of aspirin in the tablet. Compare to the
amount reported by the manufacturer, as well as to the amount calculated in the fluorometric analysis
(from next part).

4.1.4 Fluorometric Analysis of Acetyl Salicylic Acid in Aspirin Tablets

Introduction
Fluorescence is the emission of radiation from an atom or molecule, following the exposure of the atom
or molecule to electromagnetic radiation. The incident radiation excites the compound, and the
fluorescent radiation is emitted when the compound returns to the ground state.

In dilute solutions, the intensity of fluorescence is directly proportional to the concentration of the
fluorescent compound, and the calibration graph method can be used to determine concentrations.

Acetyl salicylic acid is an analgesic compound (pain-killer) that is present in aspirin tablets. These tablets
are used to delay the production of blood platelets (i.e., to delay blood coagulation/clotting). The tablets
contain other compounds, such as binding materials, pH adjusters, and coating materials. In this
experiment, the aspirin tablet will be dissolved in water and NaOH will be added to make the acetyl
salicylic acid adopt its salicylate ion form.

The salicylate ion emits fluorescent radiation around 400 nm, after excitation at 300 nm.

The instrument you will be using in this experiment is the USB 2000 Spectrometer, manufactured by
Ocean Optics. This is a compact instrument, about the size of a deck of cards, with one input port (a
fiber optic that delivers the light into the spectrometer) and a USB output port that sends the data to
the computer. Together with the dedicated software program, it is possible to see and analyze the
data.

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Light is delivered from the fiber optic and reflected off the mirror at the far end of the spectrometer. It
hits the diffraction grating and is separated into the different wavelengths that make up the light beam.
The focusing mirror focuses the light on the CCD detector. There is a correlation between the location of
the CCD and the wavelength of the photon that hits it. Therefore, the intensity of light as a function of the
location on the CCD is linearly correlated to the intensity as a function of wavelength, which is the
spectrum. The diagram above does not show the electronic parts that read the charge on the detector,
interpret it as a digital signal and output it through the USB port.

When the fiber optic is connected at a 180° angle to the sample cell, the spectrometer measures
absorbance, and when the fiber optic is connected at a 90° angle to the cell, the spectrometer measures
fluorescence (this requires prior calibration).

Experimental Procedure
Preparation of solutions for the calibration plot
1. You have at your disposal a stock solution of acetyl salicylic acid at a concentration of 0.077 g/L.
2. Mark nine 50 mL volumetric flasks: six will be used for the calibration plot and three for the samples.
Into each flask, transfer 1 mL 4 M NaOH (from a 10 mL burette).
3. Fill a 25 mL burette with the stock solution of acetyl salicylic acid (0.077 g/L).
4. From the stock solution, transfer the following volumes into the six flasks marked for the calibration
plot, respectively: 0, 1, 2, 3, 4, 5 mL. Fill the flasks with distilled water up to the marked line.

Preparation of the samples for measurement

5. Using a pipette, transfer 25 mL of the aspirin solution you prepared above (in sample preparation,
step 10) into the three volumetric flasks marked for the sample solutions (the ones already containing
NaOH). Complete the volume with distilled water.

Measuring the Fluorescence spectrum with the USB 2000 device

6. In order to measure fluorescence, verify that you use the 600 micron diameter fiber optic and make
sure it is connected at a 90° angle to the spectrometer.

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7. Turn on the lamps (UV, Vis).
8. Wait 10 minutes for the light source to stabilize thermally. In the meantime:
9. Turn on the computer and open the OOIBase32 program.
10. Before performing any measurements, load a calibration file (calibration was performed in the past),
by clicking:
File  open  experiment  fl 3100.experiment
11. Verify that you are in “mode of operation: scope”
12. Insert a quartz cuvette (CAREFULLY) with your blank solution and cover it with an appropriate lid.
13. Wait about 30 seconds for the graph to stabilize, then press the gray lightbulb icon (Global Dark) that
appears in the first row. At this point, the program saves the blank spectrum.
14. To subtract the blank spectrum from all subsequent measurements, click on the -gray lightbulb icon
(Subtract Dark Spectrum) that appears in the second row. Wait for the graph to go down to zero.
15. Insert a cuvette containing your sample. Cover it with the appropriate lid. Choose “Relative
Irradiance” mode, in order to obtain a fluorescence spectrum.
16. Click on the camera icon (Snapshot) to freeze the measurement process.
17. Move your cursor to the wavelength of maximum fluorescence and read the value. Write down the
wavelength and value in your notebook.
18. Save the spectrum in a folder with your name (in its processed form).
19. Before continuing to the next measurement, release the Snapshot icon by clicking on it again.
20. Repeat steps 15-19 for all of the calibration solutions and the aspirin samples. Do not forget to cover
the cuvettes before each measurement!
21. When you are finished, print all the spectra on the same grid (overlay) and attach to your report.

Results Analysis
1. Calculate the concentration of the stock solution of acetyl salicylic acid (M.W. 138.13 g/mole) and the
concentrations of the salicylate ion in all of the calibration solutions.
2. From the fluorescence results, draw a calibration plot of the fluorescence intensity as a function of
the solution concentration.
3. From the results of the three aspirin samples, calculate the average weight of acetyl salicylic acid in
the aspirin tablet. Compare to the value reported by the manufacturer, as well as the result from the
Conductometric Analysis.

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