Experiment 8: Titration Curve

CAROLINO, Jessa Maureen M., SARMIENTO, Dionne Marie M. Professor Kevin Anthony S. Sison College of Public Health, University of the Philippines Manila, MNL PH 1000 Abstract A titration curve is defined by a graph of the pH versus the volume of the added titrant. The shape of the graph helps to determine the equivalence point of the titration. In this experiment, titrations between (1) a weak acid and a strong base, (2) a strong acid and a strong base, and (3) a strong acid and a weak base were performed. Graphs and computations were made by the end of the experiment to fully understand the concepts and applications of the titration process. Keywords: Titration, Titration Curve, Titrant, Equivalence point Introduction Titrations are used to determine the concentration of a particular solute in a solution, which involves combining a sample of the solution with a reagent solution of known concentration. Titrations can be conducted using acid-base, precipitation, or oxidation-reduction reactions. The point at which stoichiometrically equivalent quantities are brought together is known as the equivalence point of the titration (Brown, Lemay, et.al, 2009). In graphing a titration curve, a plot is sketched between the pH, monitored by a pH meter, versus the volume of the added reagent solution of known concentration, in this case, is called a titrant.

Experimental For Part A, 25 mL of 0.1 HOAc was measured using a volumetric pipet and was transferred to a 100-mL beaker. The initial pH of the solution was determined using a pH meter. 0.1 M of NaOH acted as the titrant and was added in increments of 1 mL. The solution was mixed well using a stirring rod and the pH was recorded after each addition. When the pH changed abruptly after the last increment of titrant was added, the titrant was added in 0.5 mL increments. The titration continued until the pH reading was 5-6 units past neutral. The same procedure was done with 0.1 M HCl, with 0.1 M NaOH, and 0.1 M NH4OH, with 0.1 M HCl.

For Part B, a sample test was performed to determine if the unknown solution is an acid or a base. 25 mL of the unknown solution was measured and transferred to a 100-mL beaker. The initial pH of the unknown solution was determined using a pH meter. 0.1 M HCl, for an unknown base, and 0.1 M NaOH, for an unknown acid, acted as the titrant and was added in increments of 1 mL. The solution was mixed well and the pH was recorded after each addition. When the pH changed abruptly after the last increment of titrant was added, the titrant was added in 0.5 mL increments. The titration continued until the pH reading was 5-6 units past neutral. Results A. The following graphs show the titration curves between the acidbase reactions in Part A: I. Titration of 25 mL of 0.1 M HOAc with 0.1 M NaOH
Volume of 0.1 M NaOH VS. pH
15 10 5 0 0 5 10 15 20 25

II. Titration of 25 mL of 0.1 M HCl with 0.1 M NaOH

Volume of 0.1 M NaOH VS. pH
15 10 5 0 0 10 20 30

Volume of 0.1 M NaOH X-axis pH Y-axis III. Titration of 25 mL of 0.1 M NH4OH with 0.1 M HCl
Volume of 0.1 M HCl (mL) VS. pH
15 10 5 0 0 5 10 15

Volume of 0.1 M HCl X-axis pH Y-axis B. The following graphs show the titration curves between the acidbase reactions in Part B: I. Titration of 10 mL of an unknown solution A with 0.1 M NaOH

Volume of 0.1 M NaOH (mL) X-axis pH Y-axis

Volume of 0.1 M NaOH VS. pH

15 10 5 0 0 5 10 15

Volume of 0.1 M NaOH X-axis pH Y-axis II. Titration of 10 mL of an unknown solution B with 0.1 M NaOH
Volume of 0.1 M NaOH VS. pH
15 10 5 0 0 10 20 30

Volume of 0.1 M NaOH X-axis pH Y-axis III. Titration of 10 mL of an unknown solution C with 0.1 M NaOH
Volume of 0.1 M NaOH VS. pH
15 10 5 0 0 5 10 15

Volume of 0.1 M NaOH X-axis pH Y-axis Discussion

In Part A, the titration of 0.1 M HOAc with 0.1 M NaOH is an example of a weak acid-strong base titration. Its titration curve can be divided into four parts. The first part, namely the initial pH, is the point where 0 mL of the titrant is added to the acetic acid. Therefore the pH is entirely dependent to the pH of the 0.1 M HOAc. The second part, the halfequivalence point, is the point between the initial pH and the equivalence point. It lies within the buffer region, a region where the buffer resists large changes in pH, thus the observable flat line of the graph. The half-equivalence point is where the buffer is at its optimal capacity, meaning pH=pKa. The third part is where equimolar amounts of the titrant is added to the acetic acid. At this point, 0.1 M NaOH completely reacts with 0.1 M HOAc to form their salt, sodium acetate. It can be observed that at the equivalence point, the pH value is higher than 7. The pH at the equivalence point is always above 7 in a weak acidstrong base titration because the salt formed is a weak base. The fourth part is the region after the equivalence point. Continuous addition of the titrant, after passing the equivalence point, leads to excess amount of base. In this region, the pH is determined by the

concentration of OH- from the excess NaOH. In the next graph, the titration curve of 25 mL of 0.1 M HCl with 0.1 M NaOH can be observed. This titration is an example of a strong acid-strong base titration. In this graphs first part, the initial pH has a very low value, compared to the acetic acid. This is because HCl is a strong acid, and at this region, the pH is entirely dependent to the pH of HCl, thus a low initial pH. For the second part, the pH of the solution at halfequivalence point is determined by the concentration of HCl that has not been neutralized. And because HCl is a strong acid, the pH at the rapidrise portion of the curve near the equivalence point is higher than the acetic acid. At the equivalence point, an equal amount of 0.1 M NaOH is added to 0.1 M HCl, leaving only a solution of their salt, NaCl. The pH is expected to obtain a value of 7.00 because the cation of the strong base that is NaOH, and the anion of the strong acid that is HCl do not hydrolyze and therefore have no appreciable effect on pH. Continuous addition of NaOH results in a solution with excess base, thus the pH is determined by the concentration of the excess NaOH in the solution (Brown, Lemay, et.al, 2009).

For the last graph, the titration curve of 25 mL of 0.1 M NH4OH with 0.1 M HCl, is an example of a strong acidweak base titration. The same concepts in weak acid-strong base, applies in this type of acid-base reaction. The initial pHs value, though, depends on the pH of NH4OH, and because it is a weak base, the initial pH has a relatively high value. For the second part, at half-equivalence point, pH=pKb, since the buffer is at its optimal capacity. The third part, where equimolar amounts of 0.1 M HCl and 0.1 M NH4OH are mixed, the pH is expected to be lower than 7. The pH value is always lower than 7 in a strong acid-weak base titration because the salt formed is a weak acid. In the fourth part, at excess amount of HCl added to NH4OH, the pH is determined by the + concentration of H from the excess HCl. In Part B, three unknown acidic solutions were titrated with 0.1 M NaOH. Titration curves of each of the unknown acids were used to determine whether the solutions were weak or strong acids. For unknown solution A, the pH meter was used to determine its pH, and it showed a relatively low value. It was believed to be a weak acid, and its titration curve was used to confirm

the hypothesis. The titration curve established a similar graph to the weak acid-strong base titration curve and both showed similar features: a low initial pH appropriate for a weak acid, an equivalence point with a pH value higher than 7, and a pH value dependent to the concentration of OH- due to excess amount of NaOH. Thus, unknown solution A is indeed a weak acid. For unknown solution B, its initial pH was determined from a pH meter, and a low pH, appropriate for a weak acid, was established from the instrument. A graph was made from the titration of 10 mL of an unknown acid with 0.1 M NaOH, and a very distinct shape described its titration curve. The solution exhibited a titration curve with multiple equivalence points. When weak acids contain more than one ionizable H atom, reaction with OHoccurs in a series of steps. When neutralization steps of a polyprotic acid or polybasic base are sufficiently separated, the substance exhibits a titration curve with multiple equivalence points. For unknown solution B, two equivalence points can be observed in its graph, thus confirming that it is a weak diprotic acid.

For unknown solution C, a very low initial pH was determined from a test using the pH meter. The unknown solution was believed to be a strong acid, and since NaOH is a strong base, the titration curve of unknown solution C was compared to a titration curve of a strong acid-strong base reaction. Both reactions established similar features: very low initial pH, appropriate for strong acids, a rapid-raise portion of the curve steeper than weak-strong titrations exhibit, and a pH value dependent to the concentration of OH- from the excess amount of NaOH. Therefore, it can be inferred that unknown solution C is a strong acid. Guide Questions 1. In a separate sheet of paper, construct the theoretical titration curves for the following by plotting pH versus the volume of the titrant computed after every 5 mL of the titrant has been added. *For the following graphs: BLUE - Experimental RED - Theoretical I. 25 mL 0.1 M HOAc with 0.1 M NaOH Volume pH 0 mL 3.13 5 4.31 10 4.83

15 20

5.77 11.66

0 mL 5 10

10.3 9.30 7.86

HOAc-NaOH Titration Curve

15 12 10 5 0 0 5 10 15 20 25 10 8 6 4 2 0 0 5 10 15

NH4OH-HCl Titration Curve

Volume of 0.1 M NaOH X-axis pH Y-axis II. 25 mL 0.1 M HCl with 0.1 M NaOH Volume pH 0 mL 1.01 5 1.43 10 1.62 15 1.83 20 2.20 25 9.25 HCl-NaOH Titration Curve
10 8 6 4 2 0 0 10 20 30

Volume of 0.1 M HCl X-axis pH Y-axis Sample Computations: I. 0.1 M HOAc with 0.1 M NaOH At 0 mL NaOH: HOAC + H2O I 0.1 M C -x E 0.1-x Ka HOAC = 1.8 x 10-5 Ka =
[ [ ][ ] ] ( )( )

OAc- +H3O+ 0 0 +x +x x X

1.8 x 10-5 =

x = 1.33 x 10-3 = [H3O+] = [H+] pH = -log [H+] = -log (1.33 x 10-5) pH = 2.87 At 5 mL NaOH: Concentrations NaOH = 0.1 M = 0.1 mmol/mL x 5mL = 5mmol HOAc = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol

Volume of 0.1 M NaOH X-axis pH Y-axis III. 25 mL 0.1 M NH4OH with 0.1 M HCl Volume pH

Total Volume = (25 + 5)mL = 30 mL HOAC + OHOAc- + H2O I 2.5 0.5 0 C -0.5 -0.5 +0.5 E 2 0 0.5 Applying the Henderson-Hasselbalch equation, pH = pKa + log
[ [ ] ]

HOAC + OHOAc- + H2O I 2.5 1.5 0 C -1.5 -1.5 +1.5 E 1 0 1.5 Applying the Henderson-Hasselbalch equation, pH = pKa + log
[ [ ] ]

pH = - log (1.8 x 10-5) + log pH = 4.92 At 20 mL NaOH: Concentrations NaOH = 0.1 M = 0.1 mmol/mL x 20mL = 2 mmol HOAc = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 20)mL = 45 mL HOAC + OHOAc- + H2O I 2.5 2 0 C -2 -2 +2 E 0.5 0 2 Applying the Henderson-Hasselbalch equation, pH = pKa + log
[ [ ] ]

pH = - log (1.8 x 10-5) + log pH = 4.14 At 10 mL NaOH: Concentrations NaOH = 0.1 M = 0.1 mmol/mL x 10mL = 1 mmol HOAc = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 10)mL = 35 mL HOAC + OHOAc- + H2O I 2.5 1 0 C -1 -1 +1 E 1.5 0 1 Applying the Henderson-Hasselbalch equation, pH = pKa + log
[ [ ] ]

pH = - log (1.8 x 10-5) + log pH = 5.35 At 25 mL NaOH: Concentrations NaOH = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol HOAc = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 25)mL = 50 mL HOAC + OHOAc- + H2O

pH = - log (1.8 x 10-5) + log pH = 4.57 At 15 mL NaOH: Concentrations NaOH = 0.1 M = 0.1 mmol/mL x 15mL = 1.5 mmol HOAc = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 15)mL = 40 mL

I 2.5 2.5 0 C -2.5 -2.5 +2.5 E 0 0 2.5 Undergoing hydrolysis, OAc- = 2.5 mmol/50 mL = 0.05 M OAc- + H2O HOAc- + OHI 0.05 0 0 C -x +x +x E 0.05 x X x Kb = Kb = 5.56 x 10-10 Kb =
[ [ ][ ] ( )( ) ]

pH = - log [H+] = - log pH = 1.18 At 10 mL NaOH: Concentrations NaOH = 0.1 M = 0.1 mmol/mL x 10mL = 1 mmol HCl = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 10)mL = 35 mL H3O+ + OH2H2O I 2.5 1 C -1 -1 E 1.5 0 + + [H3O ] = [H ] pH = - log [H+] = - log pH = 1.37 At 15 mL NaOH: Concentrations NaOH = 0.1 M = 0.1 mmol/mL x 15mL = 1.5 mmol HCl = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 15)mL = 40 mL H3O+ + OH2H2O I 2.5 1.5 C -1.5 -1.5 E 1 0 + + [H3O ] = [H ] pH = - log [H+] = - log pH = 1.60 At 20mL NaOH: Concentrations NaOH = 0.1 M = 0.1 mmol/mL x 20mL = 2 mmol

5.56 x 10-10 =

x = 5.27 x 10-6 = [OH-] pOH = - log (5.27 x 10-6) = 5.28 pH = 14 5.28 = 8.72 II. 0.1 M HCl with 0.1 M NaOH At 0 mL NaOH: HCl is a strong acid. Therefore, [H+] = [HCl] = 0.1 M pH = - log [H+] = 1 At 5 mL NaOH: Concentrations NaOH = 0.1 M = 0.1 mmol/mL x 5mL = 0.5 mmol HCl = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 5)mL = 30 mL H3O+ + OH2H2O I 2.5 0.5 C -0.5 -0.5 E 2 0 + + [H3O ] = [H ]

HCl = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 20)mL = 45 mL H3O+ + OH2H2O I 2.5 2 C -2 -2 E 0.5 0 + + [H3O ] = [H ] pH = - log [H+] = - log pH = 1.95 At 25mL NaOH: Concentrations NaOH = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol HCl = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 25)mL = 50 mL H3O+ + OH2H2O I 2.5 2.5 C -2.5 -2.5 E 0 0 + [H3O ] = [OH ] = x Kw = - [H3O+] [OH-] = x2 = 1.0 x 10-14 pH = - log [H3O+] = - log (1.0 x 10-7) pH = 7 III. 0.1 M NH4OH with 0.1 M HCl At 0mL HCl: NH4OH + H2O NH4+ + OHI 0.1 0 0 C -x +x +x E 0.1-x x x [ ][ ( )( ) ] -5 Kb = = = 1.8 x 10
[ ]

pH = 14 2.87 = 11.13 At 5mL HCl: Concentrations HCl = 0.1 M = 0.1 mmol/mL x 5mL = 0.5 mmol NH4OH = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 5)mL = 30mL NH4OH + H+ NH4+ + H2O I 2.5 0.5 0 C -0.5 -0.5 +0.5 E 2 0 0.5 [ ] pOH = pKb + log
[ ]

pOH = - log (1.8 x 10-5) + log pOH = 4.14 pH = 14 4.14 = 9.86 At 10mL HCl: Concentrations HCl = 0.1 M = 0.1 mmol/mL x 10mL = 1 mmol NH4OH = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 10)mL = 35mL NH4OH + H+ NH4+ + H2O I 2.5 1 0 C -1 -1 +1 E 1.5 0 1 [ ] pOH = pKb + log
[ ]

pOH = - log (1.8 x 10-5) + log pOH = 4.57 pH = 14 4.57 = 9.43 At 15mL HCl:

x = 1.3 x 10-3 = [OH-] pOH = - log [OH-] = 2.87

Concentrations HCl = 0.1 M = 0.1 mmol/mL x 15mL = 1.5 mmol NH4OH = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 15)mL = 40mL NH4OH + H+ NH4+ + H2O I 2.5 1.5 0 C -1.5 -1.5 +1.5 E 1 0 1.5 [ ] pOH = pKb + log
[ ]

pOH = - log (1.8 x 10-5) + log pOH = 4.92 pH = 14 4.92 = 9.08 At 20mL HCl: Concentrations HCl = 0.1 M = 0.1 mmol/mL x 5mL = 0.5 mmol NH4OH = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol Total Volume = (25 + 5)mL = 30mL NH4OH + H+ NH4+ + H2O I 2.5 2 0 C -2 -2 +2 E 0.5 0 2 [ ] pOH = pKb + log
[ ]

NH4OH = 0.1 M = 0.1 mmol/mL x 25 mL = 2.5 mmol Total Volume = (25 + 25)mL = 50mL NH4OH + H+ NH4+ + H2O I 2.5 2.5 0 C -2.5 -2.5 +2.5 E 0 0 2.5 Undergoing hydrolysis, NH4+ = 2.5 mmol/50 mL = 0.05 M NH4+ + H2O NH4OH + H3O+ I 0.05 0 0 C -x +x +x E 0.05x x Ka = = = 5.56 x 10-10 Ka=
[ [ ][ ] ]

( )( )

= 5.56 x 10-10

x = 5.26 x 10-6 = [H3O+] pH = - log [H3O+] = - log (5.26 x 10-6) pH = 5.28 2. Discuss the titration curves obtained in each case in Part A. Titration of 0.1 M HOAc with 0.1 M NaOH The graph shows a titration curve between a weak acid and a strong base. At initial pH, the pH value is 3.13. As the graph progresses, a flat line can be observed as the buffer plays its role to resist changes in pH. At equivalence point, the pH obtained is higher than 7 because NaOH is a strong base. And at excess base, the pH depended on the concentration of OH- from the excess NaOH.

pOH = - log (1.8 x 10-5) + log pOH = 5.35 pH = 14 5.35 = 8.65 At 25mL HCl: Concentrations HCl = 0.1 M = 0.1 mmol/mL x 25mL = 2.5 mmol

Titration of 0.1 M HCl with 0.1 M NaOH The graph shows a titration curve between a strong acid and a strong base. At initial pH, the pH value is 1.01. As the graph progresses, a flat line can be observed as the buffer plays its role to resist changes in pH. At equivalence point, the pH is expected to obtain a value of 7 since both are strong solutions, although in this experiment, at equimolar amounts of both solutions, the pH obtained is 9.25. And at excess base, the pH depended on the concentration of OH- from the excess NaOH. Titration of 0.1 M NH4OH with 0.1 M HCl The graph shows a titration curve between a strong acid and a weak base. At intial pH, the pH value is 10.3. As the graph progresses, a flat line can be observed as the buffer plays its role to resist changes in pH. At equivalence point, the pH obtained is lower than 7, because HCl is a strong acid. And at excess acid, the pH depended on the concentration of H+ from the excess HCl. 3. Is the unknown a strong/weak acid/base? Explain your answer. Titration of unknown acidic solution A with 0.1 M NaOH At intial pH, the

pH value is 2.31. We hypothesized the unknown solution to be a weak acid, and since NaOH is a strong base, we compared its titration curve to a weak acid-strong base titration curve. Both exhibited the following features in the graph: a low initial pH, a pH value higher than 7 at equivalence point, and a pH dependent on the concentration of the anion of the strong base from the excess base. Thus, unknown acidic solution A is a weak acid. Titration of unknown acidic solution B with 0.1 M NaOH At initial pH, the pH value is 1.9. We hypothesized the unknown solution to be a weak acid since its initial pH is appropriate for a weak acid. When we graphed the titration curve, we observed that the solution exhibited multiple equivalence points. Therefore we concluded that unknown acidic solution B is a weak diprotic acid. Titration of unknown acidic solution C with 0.1 M NaOH At initial pH, the pH value is 1.65. We hypothesized the unknown solution to be a strong acid, and since NaOH is strong base, we compared its titration curve to a strong acid-strong base titration curve. Both exhibited the following features in the graph: a very low initial pH, a rapid-raise portion of the curve steeper than weak-strong

titrations exhibit, and a pH value dependent to the concentration of the anion of the strong base from the excess base. Therefore, we concluded that unknown acidic solution C is a strong acid. 4. Determine the concentration of the unknown sample. Unknown acidic solution A: M1V1 = M2V2 (0.1 M NaOH) (10 mL NaOH) = M2 (3 mL solution A) M2 = 0.33 M solution A Unknown acidic solution B: M1V1 = M2V2 (0.1 M NaOH) (10 mL NaOH) = M2 (9 mL solution B) M2 = 0.11 M solution B Unknown acidic solution C: M1V1 = M2V2 (0.1 M NaOH) (10 mL NaOH) = M2 (9 mL solution C) M2 = 0.11 M solution C Conclusion Titration curves of strong acid-strong base starts with a very low initial pH and progresses to a value of 7 at equivalence point, where equal amounts of the acid and base are mixed. At the end of the curve, the pH is determined by the concentration of OH-.

For weak acid-strong base and strong acid-weak base reactions, their titration curves starts with a low/high pH and progresses to a value higher/lower than 7 at equivalence point, where equal amounts of the acid and base are mixed. At the end of the curve, the pH is determined by either the concentration of OH- or H+/H3O+. For titrations of polyprotic acids, reactions of excess ionizable H atoms with OH- occur in a series of steps. When neutralization steps of a polyprotic acid or polybasic base are sufficiently separated, the solution exhibits a titration curve with multiple equivalence points. References Chemistry: The Central Science. 11th Edition. (2009). Brown, T., Lemay, H. E., Bursten, B., Murphy, C., Woodward, P. General Chemistry: Principles and Modern Applications. 10th Edition. (2011). Petrucci, R., Herring, F. G., Madura, J. D., Bissonnette, C.