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Experiment #4: Determination of Acid Constant, Ka

CHEMISTRY 102
May 3, 2016

Abstract

Three methods were employed in this experiment, which mainly involved titration. In the
first titration method, the pH was determined using a pH sensor; the calculated Ka was 1.67 x 10 3. In the second titration method, the pH at half equivalence point were determined from the
titration curves. The average Ka calculated was 1. 52 x 10-5. The third method was back titration
and the Ka calculated was 1.38 x 10-5. The average molarity of acetic acid in Part II was
0.0957M and 0.0514 M for Part III. Despite large fluctuations of the titration curves, the average
Ka had the value closest to the literature value of Ka which was 1.76 x 10-5.
INTRODUCTION
Acids may either be strong or weak. A strong acid will completely ionize in water while a
weak acid will partially ionize. A weak acid does not produce as much H + ions when mixed in an
aqueous solution compared to a strong acid. The ionization of a weak acid when dissolved in
water is shown in the chemical equation below
HA(aq) +H2O(l) H3O+(aq) + A-(aq)

(1)
And the equilibrium constant expression, Ka, is a quantitative measure of the strength of
an acid in a solution. The expression is written as,
Ka = [H+] [A-]

(2)

[HA]
The Ka values of weak acids are very small which indicates a larger pKa, because the
weaker acid dissociates less with its conjugate base; which means to say that the equilibrium will
favor the undissociated weak acid as shown in eq (1). From equation 2, we can derive it to give
rise to the Henderson-Hasselbach Equation,
pH = pKa + log [A-] / [HA]

(3)

In this experiment, the laboratory method used is the acid-base titration between
standardized NaOH and Acetic acid solution to determine its pH, molarity, and use these values

to calculate Ka. The titration is based on the Arrhenius theory which states that acids produce
hydrogen ions in a solution and bases produce hydroxide ions, The weak acid reacts with the
base thereby neutralizing the solution to produce water as shown in the chemical equation,
HA(aq) + OH-(aq) A-(aq) + H2O(l)

(4)

It is a relevant method which aims to help us determine the concentrations of the acid and
base involved. It is a method where a base is gradually added to the acidic solution until the
equivalence point (or end point) has been reached. That is, when the solution has turned to
slightly pink. Titration curves are developed where the volume of the titrant is the independent
variable, and the pH is the dependent variable because it changes depending on the volume of the
titrant.
In Part I, the objective was to prepare and standardize the NaOH Solution. Potassium
Hydrogen Phthalate (KHP), a monoprotic weak acid was used as the primary standard. Its
reaction with Sodium Hydroxide is as follows:
KHC8H4O(aq) + NaOH(aq) H2O(l) + NaKC8H4O4(aq)

(5)

Shelf reagents, or in this experiment, previously prepared NaOH solutions have


inaccurate molar concentrations due to NaOH being highly soluble, and can react with
atmospheric carbon dioxide during long exposures. In other words, a 0.100M NaOH solution
prepared at one time will not have the same molar concentrations when used at another time.
KHP is used to determine the exact molar concentration of NaOH by using the method of
titration. By examining equation (5) above, we can see that KHP and NaOH has 1:1 ratio. We
now understand that the number of moles of NaOH is equal to the number of moles of KHP. We

can use this to calculate the molarity of NaOH solution by using the formula M = moles / liter of
solution.
On the second part, Acetic acid is neutralized by sodium hydroxide to determine the
molarity and pH of the acetic acid solution by using the pH probe meter. The neutralization of
acetic acid solution:
CH3COOH(aq) + NaOH(aq) H2O(l) + NaCH3COO(aq)

(6)

The pH measured from the acetic acid solution can be used to determine the [H 3O+] by
using the formula,
[H3O+] = 10-pH

(7)

The average molarity of acetic acid solution is calculated, and along with the calculated
average molarity of NaOH, we can now calculate Ka by using the formula in equation (2).
Another method determining the Ka is by developing titration curves. We can assumethat
this is the most accurate method since we can observe the values of the equivalence point
volume, half-equivalent point volume, and the pH of each on the graph with the help of the
Vernier LabQuest app. The molarity, and average molarity of the acetic acid solution, and the

pKa and Ka

Figure 1. Graph showing the equivalence and half equivalence point of an acid-base titration
Source: http://www.dartmouth.edu/~chemlab/chem3-5/acid1/full_text/chemistry.html

of acetic acid is determined through calculations found on the calculations page. The halfequivalence point is the point found halfway through the equivalence point as shown in Figure 1.
Remarkably, at this point, pH = pKa, which means that we can easily calculate the Ka of
each trial by using the formula,
Ka = 10-pka

(8)

Lastly, a Half Titration is performed to determine the K a of acetic acid. In this


procedure, acetic acid solution is titrated with NaOH, then back titrated with drops of acetic
acid. This yields to a half-titrated solution at the half-equivalence point volume. This is the pKa
of the acetic acid. Results were tabulated and calculations are shown in the following pages. The
calculated Ka from different methods employed in this experiment were compared to each other,
and then to the literature value of K a of acetic acid at 25C, which is 1.76 x 10 -5 with pKa =4.75.
Furthermore, such comparisons will help us draw out a conclusion based on which methods
performed in this experiment has the most accurate values when compared to the actual K a of
acetic acid.
EXPERIMENTAL
In Part I, a known mass of KHP is mixed with deionized water and added with a few
drops of phenolphthalein indicator. Titration of KHP solution with a carefully prepared and
standardized 0.1M NaOH solution from a buret yields to a color change of light pink. This
indicates that the endpoint has been reached. The procedure is done in three trials and the molar

concentration of the base from the data from each trial is calculated and then the average molar
concentration is calculated.
For Part II, a 25.00 ml sample of acetic acid solution with drops of phenolphthalein
indicator is titrated with the standardized NaOH solution to the endpoint. Three trials were
performed and the average molarity of the acetic acid solution is calculated. The pH is
determined before commencing the titration procedure by using the pH probe. By using equation
(7) above, we can solve for [H 3O+]. We can now solve for Ka using the equation from (2) and
plug in the values of the average molarity of acetic acid, NaOH from part I, and [H3O+].
For Part III, from the titration of 25.00ml acetic acid and NaOH solution, we developed
three titration curves from three trials to determine the Molarity and K a. Using the Vernier
LabQuest with pH probe, a two point calibration with pH = 4 and pH = 7 buffers were
performed. Using the same setup in Part II, we were able to determine the pH at each endpoint in
each of the three trials through titration. By determining the equivalence point volume found in
the titration curve, we can calculate the Ka of acetic acid.
For Part IV, a 25.00 ml of 1.00M of acetic acid was titrated with prepared 1.00M NaOH
to the endpoint. Afterwards, we added drops of acetic acid (back-titrate) until the solution is
slightly acidic. Then carefully added NaOH (dropwise) to reach the endpoint again. By
transferring another 25.00 ml to the solution, we have effectively titrated 50.00 ml total of acetic
acid to the half equivalence point.
RESULTS
A 500 ml of 0.1 M NaOH soluteion was prepared by diluting 8.33 ml (calculation found
in calculations page) of 6.0 M NaOH solution with deionized water. Table 1 shows the amount of

KHP (in grams) dissolved in 50.0ml of deionized water in each of the three trials. The KHP
solution was titrated with a buret filled NaOH solution that has been previously prepared. The
volume of NaOH dispensed to reach the endpoint, or when the solution turned slightly pink, in
trial 1 = 30.0 ml, trial 2 = 44.90 ml, and trial 3 = 8.80 ml. using these collected data, we
calculated the molar concentration of each trials. As shown in Table 1.1.
Table 1. Preparation and Standardization of NaOH Solution

TRIAL

MASS of KHP

INITIAL VOLUME

1
2
3

(g)
0.5366
0.5288
0.5248

NaOH (ml)
50.0
80.0
50.0

FINAL VOLUME NaOH VOLUME USED


(ml)
20.0
35.10
41.20

NaOH (ml)
30.0
44.90
8.80

Table 1.1 Molar concentrations of the solution in each of the three trials
TRIAL
1
2
3
Average Molarity of NaOH

Moles of NaOH (mol)


0.00263
0.00259
0.00257

Molarity of NaOH (M)


0.0877
0.0738
0.0624
0.0746 M

The average molarity of NaOH is close to the intended molarity in the experiment which
is 0.100M. However, in trial 3 of Table 1, we observe that the volume of NaOH is low compared
to Trials 2 and 3. Although that is the case, the calculated molarities of each were slightly
consistent.
Using the unknown molarity of acetic acid #54 solution provided by our instructor, we
titrated it with the same standardized NaOH solution from Part I. The pH of the acetic acid
solution before titration was 2.52.

Using the formula in equation (7), the concentration of [H+] is 3.02 x 10-3.
Table 2. Titration data of Acetic Acid with the standardized NaOH solution

TRIAL

VOLUME OF

INITIAL VOLUME

ACETIC ACID

NaOH (ml)

FINAL VOLUME NaOH (ml)

VOLUME OF NaOH
USED (ml)

(ml)

1
2
3

25.00
25.00
25.00

50.00
50.00
50.00

17.70
18.21
17.89

32.30
31.79
32.11

To find the molarity, we first find the moles of the base from part 1. Since acetic acid and
sodium hydroxide react with a 1 to 1 ratio, the number of moles of NaOH = number of moles of
acetic acid. The moles of acetic acid divided by the original sample of vinegar, we find its
Molarity. The molar concentrations of acetic acid in three trials are presented in Table 2.1.
Table 2.1 Molar concentrations of acetic acid in each of the three trials
TRIAL
Moles of acetic acid (mol)
Molarity of acetic acid (M)
1
0.00241
0.0964
2
0.00237
0.0949
3
0.0024
0.0958
Ave. Molarity of acetic acid
0.0957 M
And by following equation (2), we can find Ka by plugging in the values of the average
Molarity of NaOH from part I, [H+], and average molarity of acetic acid. The Ka of acetic acid in
Part II is 2.35 x 10-3. Another way of calculating Ka in this part is by using the equation (3) and
(8), we obtained 2.34 x 10-3, which is close to the previously calculated Ka value.
For part III, we developed titration curves in each of the three trials. In a titration curve, a
base solution is added to the weak acid (the same unknown acetic acid solution in part II) until an

equivalence point has been reached. The necessary information noted in this part is shown in
Table 3.
Table 3. Equivalence point volume, half equivalence point volume, molarity, Ka and pKa
of acetic acid.
EQUIVALENCE
TRIA

POINT VOLUME

(ml)

1
2
3

17.393
30.571
6.464

HALF
pH

EQUIVALENCE

Pka

Ka

POINT VOLUME

MOLARITY OF
ACETIC ACID (M)

(ml)

9.79
9.31
9.89

8.697
15.286
3.232

4.90
4.66
4.95

1.26 x 10-5
2.19 x 10-5
1.12 x 10-5
Average = 1.52 x 10-5

0.0519
0.0912
0.0193
0.0541

The graphs produced in this part are unstable and inconsistent, save for the graph of Trial
2 which showed a slightly stable titration curve. The method used to determine the equivalence
point volume is by using the logger lite software. We can see in Graphs 1 and 3 that it is almost
impossible to tell that it is a titration curve. The equivalence point and pH were only
approximated using a ruler. Trial 2, however, although not a perfect curve, has the most stable
result among the three. The equivalence point volume was determined by using the examine
button in the software. To find the half equivalence point volumes and pKa of the three trials,
we divide the equivalence point volume and its pH by 2. Since at this point, pH = pKa, we can
use equation (8) to find the Ka of acetic acid in part III. The average Ka = 1.52 x 10 -5. The
molarity of acetic acid in each trial is calculated by multiplying the NaOH used (ml) by its
molarity (0.0746M) and dividing it by the original sample of acetic acid (25.00ml).

Graph 1. Acetic acid solution titrated with NaOH solution (Trial 1)

Graph 2. Acetic acid solution titrated with NaOH solution (Trial 2)

Graph 3. Acetic acid solution titrated with NaOH solution (Trial 3)

For Part IV, we have performed a back titration and determined the pH by using the pH
probe. As stated earlier, at half equivalence point volume, pH = pKa. These values were
recorded in Table 4.
Table 4. pKa and Ka of half titration trials
Trial
1
2

pH at Equivalence point
9.19
9.48
Average Ka

pH at Half

pKa

Ka

Equivalence point
4.85
4.87

4.85
4.87

1.41 x 10-5
1.35 x 10-5
1.38 x 10-5

In this part, we observed that the pH at half equivalence point may have a 0.02
difference, but the Ka has about 1 x 10-6 difference between the two trials. The average Ka in part
III and IV, however, are slightly close to each other but are not sufficiently close to the literature
value of the Ka of acetic acid. The Ka calculated in part I came nowhere near the literature value.
DISCUSSION
The Bronsted Lowry theory states that an acid is a substance which donates a proton,
and a base is a substance which accepts a proton. Based on the experiments conducted, we have
visually observed the neutralization of an acid-base solution via titration, and hence, a better
understanding of the Arrhenius theory and the Bronsted Lowry theory. The indicator used in
this experiment is phenolphthalein. At equivalence point, the number of moles of base is equal to
the number of moles of acid, in other words, the solution has been neutralized exhibiting a slight
pink colorization.
In this experiment, the class analyzed the acetic acid solution, a weak acid, when titrated
with a strong base (NaOH solution). NaOH ionized completely in the water, forming a high

concentration of OH- (pH > 7 as shown in all tables in this experiment). On the other hand, acetic
acid partially dissociated in water, thereby forming low concentrations of H+ ions.
First of all, it was noted that the room temperature where the experiment took place was
measured to be around 20C. This means that the Ka values obtained in this experiment may be
slightly different to the literature value of Ka of acetic acid at 25C, which is 1.76 x 10-5.
In part I, the preparation and standardization of NaOH was employed, and the KHP
solution was titrated with it. The volume of NaOH used was 8.33 ml, yielding to an average
molarity of the NaOH solution to be 0.0746 M. The measurement of the NaOH volume may not
be perfectly accurate which can greatly affect the calculated Molarity of NaOH.
In part II, we used the pH sensor to determine the pH of acetic acid before titration. From
the determined pH, the calculated [H3O+] concentration was 3.02 x 10-3. The calculated Ka is
2.35 x 10-3. This value has greatly deviated from our literature value, and we can only note that
the method employed in this part was not accurate. This may be because of the fact that the
standardized NaOH may not have been accurately measured after the titration was completed,
and that the molarity of the solution was not accurately determined in part I. Another discrepancy
involved on this part was our own discretion of deciding when the solution has stabilized. The
pH shown in the Vernier labquest app during that time was notably changing.
The results obtained in part III was obviously far from being successful. First of all, the
NaOH used in this part was stored for a few days and may have reacted with atmospheric carbon
dioxide. This means the molarity of my standardized NaOH was not the same as the day I
prepared it. The titration curves developed in Trial 1 had various large fluctuations and Trial 3
developed an unsuccessful curve as well. Trial 2, however, developed the most stable titration

curve among the three, but it is not safe to say that this trial was successful. Arguably, the pH at
half equivalence point volumes in Trial 1 and 3 were manually determined due to it being
impossible to detect at the loggerlite software. As mentioned above, pH = pKa at half
equivalence point. The values were determined as accurately as possible to calculate the Ka of
acetic acid in each trial. The average Ka in part III was calculated to be 1.52 x 10

-5

despite the

huge discrepancies. There is a possibility that the Ka would be as close to the Ka literature value
if the titration was performed correctly. I planned to do more trials but due to insufficient amount
of NaOH solution, I have not done so. If there is one thing in common among the three trials, it
is that in the titration curve, we have seen a huge increase in the pH when more base was added
after the equivalence point in the solution. But overall, the results in part III were unreliable even
though the calculated average Ka came close to the literature value.
Lastly, in part IV, the Ka of acetic acid was determined through back titration of the
same acetic acid solution ( 994.30.2x 10-3) but a different prepared NaOH solution
(1.0153M)0with the pH sensor. At half equivalence point, where half the acetic acid present
were converted into the acetate ion, a conjugate base, the pH = pKa. This was the easiest method
among the three, and have provided a Ka value of 1.38 x 10 -5. This was close to the literature
value, but not quite.
For the morality of acetic acid in part II, the calculated value was 0.0957 M; the molarity
of acetic acid in part III was 0.0541M. As expected, the molarities of acetic acid in Part III are
inconsistent just by looking at the titration curves. The molarity might be inaccurate due to
inaccurate measurements of the solution. Furthermore, the NaOH solution remained in the shelf
for days through which its molarity can change over time.

Based on the observed results, the Ka calculated in part II and III came close with the
literature value. Considering that the room temperature was less than 20C, we can assume that
the Ka value is an acceptable value. However, when comparing the three methods, back titration
was the easiest to perform, but the titration curves provided in Part III had a value close to the
literature value with Ka = 1.52 x 10 -5 despite the unstable and unreliable generated titration
curves. It would have been more accurate if the titration was done successfully
Despite the unsuccessful titration in some parts, the results were in agreement with the
Arrhenius and the Bronsted Lowry theory, where acids produce hydrogen ions and are proton
donors, whereas bases produce hydroxide ions and are proton acceptors. The conjugate base of
acetic acid, the acetate ion, is in equilibrium with the weak acid after sufficient amount of NaOH
was titrated to the acid solution.
In order to improve this experiment, Parts I, II, and III should be done all on the same day
to ensure that the molarity of the standardized NaOH solution will be the same. Also, we should
be keener in observing the first time the color of the solution has changed, considering that some
of us have overdone the titration causing the solution to become dark pink. This can greatly
affect the molarity of the solution.