Acid-Base Titrations

Exp. 4
CHM1311[C]
Nov. 14th, 2017

Joseph Ostrovsky
8608232
+3 Bonus points for second place
Contents
Introduction ..................................................................................................................................... 3
Procedure ........................................................................................................................................ 5
Data and Observations .................................................................................................................... 6
Raw data ...................................................................................................................................... 6
Points of Equivalence (mL of added NaOH) ............................................................................ 12
Calculations................................................................................................................................... 12
Discussion ..................................................................................................................................... 14
Conclusion .................................................................................................................................... 16
References ..................................................................................................................................... 17

Table of figures

Figure 1-pH of run 1 of titration of HCl with NaOH ...................................................................... 6

Figure 2-Derivative (pH/s) of run 1 of titration of HCl with NaOH .............................................. 7
Figure 3-pH of run 2 of titration of HCl with NaOH ...................................................................... 7
Figure 4-Derivative (pH/s) of run 2 of titration of HCl with NaOH .............................................. 8
Figure 5-pH of run 1 of titration of diprotic with NaOH ................................................................ 8
Figure 6-Derivative (pH/s) of run 1 of titration of diprotic acid with NaOH ................................. 9
Figure 7-pH of run 2 of titration of diprotic with NaOH ................................................................ 9
Figure 8-Derivative (pH/s) of run 2 of titration of diprotic acid with NaOH ............................... 10
Figure 9-pH of run 1 of titration of citrate sample with NaOH .................................................... 10
Figure 10-Derivative (pH/s) of run 1 of titration of citrate sample with NaOH ........................... 11
Figure 11-pH of run 2 of titration of citrate sample with NaOH .................................................. 11
Figure 12-Derivative (pH/s) of run 2 of titration of citrate sample with NaOH ........................... 12

Table 1-Points of equivalence in titration of HCl with NaOH ..................................................... 12

Table 2-Points of equivalence in titration of diprotic acid with NaOH ........................................ 12
Table 3-Points of equivalence in titration of citrate sample with NaOH ...................................... 12
Introduction

The concentration of a solution is measured in moles per litre (M), i.e. = , where c is the
concentration in mol/L, n is the amount of moles, and v is the volume is litres. Given the
concentration and volume, the number of moles can be calculated using the formula = . Since
the addition of water to the solution does not change the amount of moles present, the ratio between
concentrations and volumes will be identical (i.e. 1 1 = 2 2 = ).
Ions within a solution have certain properties depending on their charge and electronegativity,
which determine the magnitude of their ability to repel or attract elementary electric charges (i.e.
protons and electrons) present or added in the solution. These range from attraction of negative
charges (i.e. base) to a repelling (i.e. acid) to a neutrality, both attracting and repelling equally (e.g.
salts and water).
Several attempts were made over the years to qualify this attraction with a formal definition.
Arrhenius first proposed that any substance that released proton (i.e. hydrogen ions) into a solution,
creating an ion that was strongly negative in charge, be defined as an acid, while a substance that
released hydroxide, the polar opposite of hydrogen ions, creating an ion strongly positive, be
defined as a base.

3() + + 3() is the behaviour of a typical Arrhenius acid, while
+
+ describes that of a typical Arrhenius base.

This excluded, however, those strongly electronegative ions that did not contain hydroxide.
Bronsted and Lowry extended the definition to include as a base any substance which contains an
ion that will bond with hydrogen when the substance is dissolved in water. The discovery of
molecules containing no hydrogen ions but still acting as acids further required a redefinition of
the concept. The most recently accepted solution is the definition of Lewis, which states that any
substance capable of donating an electron pair when dissolved is a base, while those that accept
electron pairs are acids.
Since a molecule on its own cannot donate or accept electrons without a dissociation process, the
strength of an acid or base depends on its solubility equilibrium (i.e. the extend to which it
dissociates to produce ions when dissolved). The less of the original substance remains, the more
ions exist to receive or lose electrons pairs.
pH is a measurement of the concentration of electron pair receivers present in a solution. Since
extremely small quantities of concentration are being used, the implementation of a logarithmic
scale (i.e. converting each order of magnitude into a linear series) simplifies matters. Since in this
experiment, only Arrhenius acid and bases will be used, the equation log[ + ] is used in
calculating pH, where [H+] is the concentration of hydrogen ions. It ranges from 0, meaning
strongly acidic, through 7, the neutrality point, up to 14, strongly basic.
A concept known as a dissociation constant Ka for acids or Kb for bases can be used to analyze the
[ ][3 + ] [+ ][ ]
strength of an acid. = []
and = []
. The higher the K value, the more the
substance dissociates, since the equilibrium favours the product more so than the reactant.
Since an acid acts as an electron pair receiver and a base as an electron pair donator, it can be
expected that a meeting of the two in equal proportion relative to the quantity of electron pairs
capable of being donated or accepted by them will result in all pairs being exchanged and the
remaining solution becoming neutral. Indeed, this process is referred to as neutralization, and
produces and neutral salt and water, both with a pH of 7. In the examples of the acid and base
given above, that process would look as follows:
3() + 2 + 3

The process of titration relates to this neutralization process. We can determine the concentration
of an acid or base by determining the required amount of its counterpart to be added for the solution
to reach a neutral pH. At the equivalence point, the pH of the solution is expected to be the same
as that of water (i.e. 7) and therefore the number of hydroxide ions and hydrogen ions are also
expected to be equal. T the equivalence point is expected to be at the point where the number of
molecules of the acid is proportional to the number of molecules of the base using the polyprotic
nature of the acids to determine the stochiometric constant.
The midpoint of a titration of a weak acid is volume of added base at which the concentration of
base added is equal to half of the original concentration of acid. At this point, the concentration of
conjugate base ions is equal to the concentration of undissolved acid substance remaining.
If + 2 + , then at the equivalence point

=


=

The equivalence point can be determined using an indicator, a substance, usually weakly acidic,
that changes colour depending on the pH of the solution. This occurs because the presence of a
base decreases the concentration of hydrogen ions in the solution to zero at the equivalence point,
leading to the weak acid dissociating more in accordance with Le Chateliers principle, in that it
reacts in the opposite direction by releasing more hydrogen. Its non-hydrogen ionic component
would have a visible colour, leading to the solution changing appearance as the pH does. Since it
is a weak acid, it does not affect the pH of the solution substantially. In this experiment, the
indicator used is phenolphthalein (C20H14O4), which becomes purple as the solution alkalizes.
Special note must be taken of polyprotic acids, since those react with bases in steps, each step
producing a weaker acidic compound to react. To simplify calculations, it is assumed that each
compound fully dissociates before the next begins reacting. Each step would then have its own
equivalence point. In general:
3 + + + 2 + 2
2 + + + 2 + + 2 + 2
2 + + 2 + 3 + + 3 + 2

Procedure
1. Add approximately 4-5 mL of 6.00 M NaOH to 245 - 250 mL of distilled water in a 400
mL beaker
Calibrating the Drop Counter
2. Attach the Drop Counter to an L bar and connect to the DG1 port of the LabQuest 2.
3. Use a universal clamp to secure the plastic buret above the detector of the Drop Counter.
Close both taps.
4. Fill the plastic buret to the 30 mL mark with dilute NaOH solution (from step 1), then
place a 10 mL graduated cylinder under the tip (and also below the detection region of
the Drop Counter).
5. Open the bottom tap on the plastic buret completely and then slowly open the top tap
until the dilute NaOH is dropping at a rate of 1-2 drops/second.
6. Add approximately 2-3 mL of distilled water to the 10 mL graduated cylinder. Note
down the exact volume in the cylinder (to one decimal place).
7. To calibrate the Drop Counter, tap Volume and select Calibrate.
8. Tap Calibrate Now and then open the bottom tap on your plastic buret completely.
9. 15. After allowing about 2 mL of dilute NaOH to flow from the plastic buret into the 10
mL graduated cylinder, close the bottom tap.
10. Enter the Precise Volume in the designated box of your LabQuest 2 and tap OK.
Standardizing the Diluted NaOH Solution
11. Obtain a glass buret and label it acid. Attach the buret to the L bar using a double buret
clamp
12. Use a 50 mL beaker to obtain approximately 25 mL of the standard monoprotic acid.
13. Fill the glass buret with the standard acid using a funnel if needed. Verify that it is not
leaking. Flow 1-2 mL of the acid through the tip of the buret, into a beaker, to ensure that
there is no air trapped in the tap.
14. Record the initial buret reading and then transfer approximately 10 mL of the standard
acid into a clean 150 mL beaker. NOTE the EXACT final reading on the buret and
calculate the EXACT volume of acid that was transferred.
15. Add 2-3 drops of phenolphthalein and a magnetic stir bar to the beaker.
16. Place the beaker of acid on a stir plate such that the solution from the plastic buret will
drop into the beaker.
17. Connect the pH probe in the CH1 port of the LabQuest 2.
18. Rinse the tip of the pH probe with distilled water and pass the pH probe through the hole
in the Drop Counter.
19. Refill your plastic buret to the 30 mL mark with dilute NaOH.
20. Start the run and then open the bottom tap completely to allow the base to flow into the
beaker at the rate of 1-2 drops/second.
 21. Note the volume of added base at which the colour of the acid solution changes.
22. Stop the run after the pH has risen and then levelled off at about pH 11-12.
23. Remove the pH probe and stirrer from the solution and rinse them with distilled water.
24. Once again, fill the plastic buret to the 30 mL mark with dilute NaOH.
25. Repeat the experiment at least once more.
26. Use a 50 mL beaker to obtain a 25 mL sample of the unknown diprotic acid.
27. Fill the clean glass buret with your unknown acid and flow 1-2 mL of the acid through
the tip, into a beaker, to ensure that there is no air trapped in the tap.
28. Repeat steps 11-25 using the standardized NaOH solution.
29. Repeat Steps 26-28 using the unknown juice sample as the acid.

Data and Observations

Raw data
Note: Due to an error in the pH probe, a pH of 7 appears as 5.85

Figure 1-pH of run 1 of titration of HCl with NaOH

Figure 2-Derivative (pH/s) of run 1 of titration of HCl with NaOH

Figure 3-pH of run 2 of titration of HCl with NaOH

Figure 4-Derivative (pH/s) of run 2 of titration of HCl with NaOH

Figure 5-pH of run 1 of titration of diprotic with NaOH

Figure 6-Derivative (pH/s) of run 1 of titration of diprotic acid with NaOH

Figure 7-pH of run 2 of titration of diprotic with NaOH

Figure 8-Derivative (pH/s) of run 2 of titration of diprotic acid with NaOH

Figure 9-pH of run 1 of titration of citrate sample with NaOH

Figure 10-Derivative (pH/s) of run 1 of titration of citrate sample with NaOH

Figure 11-pH of run 2 of titration of citrate sample with NaOH

Figure 12-Derivative (pH/s) of run 2 of titration of citrate sample with NaOH
Points of Equivalence (mL of added NaOH)
Table 1-Points of equivalence in titration of HCl with NaOH

Run 1 Run 2 Average Value

LabQuest 2 6.947 7.970 7.459
Visual Observation 6.0 6.0 6.0

Table 2-Points of equivalence in titration of diprotic acid with NaOH

Run 1 Run 2 Average Value

LabQuest 2 9.478 9.262 9.37
Visual Observation 7.0 7.0 7

Table 3-Points of equivalence in titration of citrate sample with NaOH

Run 1 Run 2 Average Value

LabQuest 2 10.45 9.532 9.991
Visual Observation 9.0 8.5 8.75

Calculations
1. Using the equations and procedures explained in the introduction, we can calculate the
approximate concentration of NaOH, given that 5 mL of NaOH were added to 250 mL of
water.
 1 1 = 2 2

(6.00 ) (0.005) = 2 (0.005 + 0.250)

0.030 2 (0.255)
=
0.255 0.255

(0.118 ) = 2

The approximate concentration of the sodium base is 0.118 M.
2. 9.85 mL of acid were added to 0.100 mL of water.
1 1 = 2 2 [1]
(0.100)(0.00985) = 2 (0.100)
(0.100)(0.00985)
= 2 (0.100)
0.100
0.00985

=
=

=

(0.00985)(0.100)
=
0.0074585
= 0.132
The more precise figure for the concentration of NaOH is 0.1321 M.
3. Since the unknown acid is diprotic, its reaction with NaOH will be as follows:
2 + 2 2 + 22

=

2 =
2 =
2
=

2(0.132)(0.00937)
=
(0.100)
= 0.025
The concentration of the unknown acid is 0.025 M.
4. Since the acid (citric) in the juice is triprotic, its equilibrium at the equivalence point with
NaOH will be as follows:
3 6 5 7 + 3 3 6 5 7 + 32

=

3 =
3 =
3
=

 3(0.132)(0.00999)
=
(0.100)
= 0.040
5.
There is a factor of 1000 in the equation for mass percent of acid since the density is
measured in grams per millilitre, while the molarity is measured in moles per litre. Since
one litre contains 1000 millilitres, a conversion factor of 1000 mL in a litre is required to
compare the two variables in a single equation.

( ) ( )
= 100%

( ) 1000

(0.040 ) (192.124 )
= 100%

(0.9982 ) 1000
= 0.769%
There was a slight discrepancy between the approximated values for the concentration of the
sodium hydroxide (0.118 mol/L) and the more exact value determined from the acid-base titration
(0.132 mol/L). This gives the error calculation

0.132 0.118
= 100%

0.132
= 0.109765329 100%
= 10.97%

Discussion
The results are mostly as expected based on the theory. The pH of an acidic solution increased as
a basic substance was dropped into it, with the equivalence point (i.e. the maximum of the
derivative) being around a pH of 7. The stronger and more monoprotic the acid, the sharper the
titration curve, likely because the polyprotic acids must undergo several internal stages during the
titration, while the weaker acids more slowly dissociate to release hydrogen ions.
1. The volume of concentrated NaOH used does not matter so long as the concentration is
known. The equivalence point between an acid and a base occurs when the number of
electron pair donors (i.e. bases) and electron pair receivers (i.e. acids), or when the number
of moles of the acid is proportional using stochiometric constants to the number of moles
of the base. Since the only factor required to establish equivalence is the number of moles,
and this can be determined knowing only the concentration of a given sample, the volume
is irrelevant in the experiment.
2. The concentration of NaOH is determined just before it was used because we can determine
it to more accuracy. Even though the concentration remains the same for any sub-volume
of the original, the larger volume being used for the base before parts of it are removed
allows for more significant digits to be used in calculating the concentration. As well, it is
 possible that evaporation of the base occurred during the experiment, decreasing the water
component, and increasing the concentration of NaOH. This would have the effect of
decreasing the volume of base needed for titration, therefore increasing the calculated
concentration of acid.
3. The volumes at equivalence point determined by LoggerPro are consistently larger that
those observed in the reduction of volume in the burette. This is likely due to an error in
measuring the reduction of volume during the calibration phase, leading to the LabQuest 2
equipment to overestimate the size of a single drop of base solution.
4. Based on the observed data, the assumption stated in the introduction that each reaction in
a polyprotic titration proceeds after the previous is completed is unwarranted, since there
is only one sharp peak in the derivative of the juice titration. This indicates that only one
equivalence point was reached. The values of Ka are obtained from Averill & Eldredge,
2007.
a. At 0 mL of base-3 6 5 7 + 2 2 6 5 7 + 3 +
The ratios of products and reactants can be determined using the constant Ka
[3 + ][2 6 5 7 ]
7.4 104 =
[3 6 5 7 ]
Since the concentrations of dihydrogen citrate and hydronium are equal,
[2 6 5 7 ]2
7.4 104 =
[3 6 5 7 ]
7.4 104 [3 6 5 7 ] = [2 6 5 7 ]
0.027202941[3 6 5 7 ] = [2 6 5 7 ]
b. At first midpoint
3 6 5 7 + 2 + + + 2 6 5 7 + 2 + 3 +
The concentrations of trihydrogen citrate, dihydrogen citrate and sodium hydroxide
would be equal.
c. 2 6 5 7 + 2 + + + 2+ + 6 5 72 + 2 + 3 +
At the first equivalence point, the concentrations of sodium would be equal to
those of dihydrogen citrate and hydrogen citrate combined, and there would be no
trihydrogen citrate present in the solution, since it has a pH of 7.
The ratio of dihydrogen citrate and hydrogen citrate can be determined using the
Ka constant.
[3 + ][2 6 5 7 ]
1.7 105 =
[2 6 5 7 ]
Since the concentrations of dihydrogen citrate and hydronium are equal,
5
[6 5 72 ]2
1.7 10 =
[2 6 5 7 ]

1.7 105 [2 6 5 7 ] = [6 5 72 ]

0.00412310563[2 6 5 7 ] = [6 5 72 ]
 The greater discrepancy between the two concentrations indicates that this
dissociation produces a weaker acid.
d. At the second midpoint
2 6 5 7 + 2 + 2+ + 6 5 72 + 2 + 3 +
The concentrations of dihydrogen citrate and hydrogen citrate would be equal,
while sodium would be double.
e. 6 5 72 + 2 + + 2 + 3+ + 6 5 73 + 2 + 3 +
At the second equivalence point, the concentrations of sodium would be equal to
those of hydrogen citrate and citrate combined, and there would be no trihydrogen
or dihydrogen citrate present in the solution, since it has a pH of 7.
The ratio of hydrogen citrate and citrate can be determined using the Ka constant.
[3 + ][6 5 73 ]
4.0 107 =
[6 5 72 ]
Since the concentrations of citrate and hydronium are equal,
[6 5 73 ]2
4.0 107 =
[6 5 72 ]

4.0 107 [6 5 72 ] = [6 5 73 ]

0.000632455532[6 5 72 ] = [6 5 73 ]
The greater discrepancy between the two concentrations indicates that this
dissociation produces a weaker acid.
f. At the second midpoint
6 5 72 + 2 + 3+ + 6 5 73 + 2 + 3 +
The concentrations of dihydrogen citrate and hydrogen citrate would be equal,
while sodium would be triple.
g. 6 5 72 + 2 + + 3+
At the third equivalence point, the concentrations of sodium would be equal to that
of citrate, and there would be no compounds of citrate and hydrogen present in the
solution, since it has a pH of 7.
It is possible that different quantities of the same acid were measured in between trials, despite
effort to ensure that identical measurements were used. If too much acid was used, this would have
the effect of increasing the volume of base needed for titration, and increasing the resulting
concentration figures for the unknown acids, while decreasing for the base. Too little acid would
decrease the volume of base needed, and increase the resulting concentration figures for the
unknown acids, while decreasing for the base.

Conclusion
The concentration of sodium hydroxide solution used in the experiment was determined to be
0.132 M; that of the unknown diprotic acid was determined to be 0.025 M; and that of the citric
acid present in the juice sample was determined to be 0.040 M, resulting in an acid composition
of 0.769%.

References
Averill, Bruce, and Patricia Eldredge. Chemistry: Principles, Patterns, and Applications.
Benjamin Cummings, 2007.