Expt # 8: Titration Curves Nicole S. Natanauan Group # 8, Chem 18.1, AB1, Mr. Julius Andrew P.

Nuez May 16, 20011 Abstract The focus of this experiment is all about titration curves. It involved the process of reacting a titrant with an analyte to its equivalence point. The pH measures gathered from the incremental additions of the titrant to the analyte and their respective volumes was used to graph the different titration curves. The scope of the experiment covered different types of titration curves namely the weak acid-strong base, weak base-strong acid and strong acid-strong base titrations. The results obtained showed the differences and similarities in the characteristics of the different titration curves and from the calculations done using the Henderson-Hasselbalch equation, theoretical titration curves were also constructed. This experiment shed some light on the concepts behind titration and titration curves. It showed the different trends of the different titration curves and the factors that caused these trends. The conclusions ultimately led to a better understanding and a greater appreciation of the titration process and its applications in the different fields of studies. Keywords: buffering region, half-equivalence point, hydrolysis, Henderson-Hasselbalch equation Introduction In an acid-base titration a solution containing a known concentration of base is slowly added to an acid or acid added to the base. Indicators can be used to signal the equivalence point of a titration or the point at which stoichiometrically equivalent quantities of acid and base have been brought together. Alternatively, a pH meter can be used to monitor the progress of the reaction producing a pH titration curve, a graph of the pH as a function of the volume of the added titrant (LeMay, 2000). The Henderson-Hasselbalch equation used in the experiment is generally used for the derivation of pH using the acid dissociation constant or pKa. The aim of this experiment is to titrate successfully the analyte with the titrant and to construct an experimental titration curve closest to its theoretical counterpart and to compute for values in terms of theoretical titrations. Experimental For Part A, in order to construct a titration curve for the weak acid-strong base and weak base-strong acid titrations, 25mL of the appropriate analyte was first measured. Using a pH meter, the initial pH of the the analyte was measured then an 1mL incremental addition of the titrant was added to the analyte continuously monitoring the pH after each addition and when the pH changed abruptly, the increments were deduced to 0.5mL. This process was repeated until the pH reading were 5 to 6 units past neutral. The process was repeated for the other

titration sample (strong acid-strong base was not performed). For the analysis of the unknown in Part B, 25mL of the unknown sample was first tested whether it was an acid or a base. Once this was established, the appropriate titrant was added to the unknown analyte in increments of 1mL until the pH changed abruptly and the addition was again deduced to 0.5mL until reading was 5 to 6 units past neutral. The pH change was carefully monitored after each addition and was noted down .And from this data, the necessary information to construct the unknown samples titration curve was established. Results These are the values obtained in the titration of 0.1M HOAc with 0.1M NaOH as shown in the constructed titration curve:

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This graph shows the pH change of the analyte 0.1M NH4OH vs the addition of the titrant 0.1M HCl in terms of volume:

For Part B, these were the data gathered represented in its titration curve:

Discussion In Part A, the graph of the weak acid HOAc and strong base NaOH has distinct features that differentiate it from the other titration curves. One of these features is the low initial pH that holds true for that of the weak acid HOAc for this initial pH is dependent entirely on the concentration of the analyte. But as the titrant NaOH is added, an abrupt change in pH is observed as the first few drops of the titrant is added but after this abrupt change a relatively flat line is observed. This is due to the fact that initially, the buffer has not yet been set up but as the graph reaches the buffer region where the buffer capacity of the weak acid is effective, the buffer plays its role and resists the pH change thus the observable flat line. This also defines the buffer range of the given buffer which in this case is the acetic acid-acetate buffer. Also located in this region and another unique feature of a weak-strong titration is the half-titration point

or half-equivalence point. This is the point where the buffer is at its optimal capacity meaning pH=pKa. The pH between the initial pH and the equivalence point is determined by the concentration of the acid that has not yet been neutralized acid. As the curve nears the equivalence point, the point where equimolar amounts of the acid and base have reacted, the graph suddenly surges up because it already passed the buffer region. And it is in this steep change that the equivalence point is located. It can also be observed that for this particular type of titration the pH at equivalence point is always greater than 7 this is due to the hydrolysis of the basic salt NaOAc that will form at the equivalence point. After the equivalence point, the pH of the solution is dependent mainly on the excess OH- ions from the extra NaOH added. The next graph shows the titration curve of the weak base NH4OH with the strong acid HCl acting as the titrant. It resembles an inverted weak acid-strong base titration curve with its initial pH instead that of a weak acid it now starts at a pH that of a weak base. It also shows the abrupt change at the start and the relatively flat line thereafter that it is caused by the buffer region. This type of titration curve also has a half-equivalence point. And again just like its counterpart, nearing its equivalence point it shows a sudden steep drop in its pH. The pH at its equivalence point is lower than 7 because of the hydrolysis of the acidic salt NH4Cl formed. After this part, the pH will be dependent on the concentration of excess HCl added. Lastly, the unknown was identified by measuring its initial pH using a pH meter, having established initially that it is a strong acid its titration curve was graphed to confirm this hypothesis. Since NaOH is the titrant used and it is a strong base, this titration curve is a strong acid-strong base titration curve. And indeed the graph has the following features that undoubtedly make the unknown a strong acid. First, its initial pH is very low appropriate for a strong acid, it does not exhibit that abrupt change then flat line that can usually be observed in a weak-strong titration curve. Also the sudden rise observed in the graph is steeper compared to its weak counterpart then after the equivalence point of 7, the pH will be dependent on the excess NaOH added. Guide Questions and Answers 1. In a separate sheet of paper construct the theoretical titration curves for the

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following by plotting pH versus the volume of the titrant computed every 5mL of the titrant has been added. A. 25mL 0.1M HOAc with 0.1M NaOH Sample Computations: HOAc + H2O H3O+ + OAcInitial 0.1 M 0 0 Change -x +x +x Equilibrium 0.1-x x x Ka= [H3O + ] [OAc-] = 1.8 x 10 -5 [HOAc] 2 -5 x / (0.1-x)= 1.8 x 10 -3 -3 x= 1.3 x 10 pH= -log (1.3 x 10 ) = 2.89 pH before equivalence point Addition of 10 mL O.1 M NaOH 0.1 M NaOH = 0.1 mol NaOH/ 1L= 0.1 mmol/ml 10 ml NaOH x 0.1 mmol/ml = 1 mmol 25 ml HOAc x 0.1 mmol/ml= 2.5 mmol HOAc + OH Initial
-

Kb = [OH] [HOAc] / [OAc] -10 2 5.6 x10 = x / 0.05-x -6 x= 5.27 x 10 pOH= -log (5.27 x 10 -6) pH= 14-5.28= 8.72 Kb = Kw/Ka Kb = 1 x10 -14 / 1.8 x 10 -5 =5.6 x10 -10

pOH=5.28

pH after equivalence point Addition of 40 mL 0.1 M NaOH 40 ml NaOH x 0.1 mmol/ml= 4 mmol 25 ml HOAc x 0.1 mmol/ml= 2.5 mmol HOAc + OH OAc Initial Change Equilibrium 2.5 mmol -2.5 mmol 0 4 mmol -2.5 mmol 1.5 mmol +2.5 mmol 2.5 mmol

+ H2O

OAc

+ H2O

2.5 1 mmol mmol Change -1 -1mmol +1mmol mmol Equilibrium 1.5 0 1mmol mmol Using the Henderson-Hasselbach equation: pH= pKa + log ( [conjugate base]/[acid]) pH= -log (1.8 x 10 [1.5 mmol/35mL]) pH= 4.57
-5

From excess OH- : pOH = -log[OH-] = -log [1.5 mmol / 65mL] = 1.64 pH = 14 1.64 = 12.36 Volume 0 5 10 15 20 25 30 35 40 45 50 55 60 B. 25mL 0.1M HCl with 0.1M NaOH pH 2.89 4.14 4.56 4.92 5.34 8.72 11.96 12.22 12.36 12.46 12.52 12.57 12.61

) + log ([1mmol/35 mL] /

pH at equivalence point Addition of 25 mL 0.1 M NaOH 25 ml NaOH x 0.1 mmol/ml= 2.5 mmol 25 ml HOAc x 0.1 mmol/ml= 2.5 mmol HOAc + OH OAc + H2O Initial Change Equilibrium 2.5 mmol -2.5 mmol 0 2.5 mmol -2.5 mmol 0

+2.5 mmol 2.5 mmol HOAc +OH 0 +x +x 0 +x +x

-

OAc Initial Change Equilibrium

H2O

2.5 mmol/ 50mL -x 0.05 M-x

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Volume pH 0 5 10 15 20 25 30 35 40 45 50 55 60 1 1.18 1.37 1.6 1.95 7 11.96 12.22 12.36 12.46 12.52 12.57 12.61 C. 25mL o.1M NH4OH with 0.1M HCl Volume pH 0 5 10 15 20 25 30 35 40 45 50 55 60 11.11 9.85 9.43 9.07 8.65 5.28 2.04 1.78 1.64 1.54 1.48 1.43 1.39

2. Discuss the titration curves obtained in each case in Part A. Titration Curve of 0.1M HOAc with 0.1M NaOH Since this is a titration of a weak acid-strong base, the graph starts with a weak pH level of about 3. At the start of the graph, an abrupt change in pH can be observed. But as the curve progresses, a relatively flat line can be observed because the buffer had already been set up. And as it nears the equivalence point, the graph surges up meaning the concentration of both the titrant and analyte are almost the same. And since NaOH is a strong base, at equivalence point the graph exhibits a pH slightly higher than 7 and after this point the pH will be dependent from the OH- ions from NaOH. Titration Curve of 0.1M HCl with 0.1M NaOH This titration of a strong acid and a strong base starts with a low pH that is dependent mainly on the concentration of the acid HCl but as the titrant is added it shows a slow increase in its pH but as it reaches the equivalence point it exhibits a steep rise of pH (steeper than what you would expect from a weak acid-strong base titration). Theoretically, the equivalence point is 7 in a strong acid-strong base + titration because Na and Cl ions do not hydrolyze. After this point, the pH will be dependent on the excess OH- from the extra NaOH added. Titration Curve of 0.1M NH4OH with 0.1M HCl The graph of weak base-strong acid resembles the weak acid-strong base titration curve but its pH initially about 11. A rapid drop can be observed upon addition of the strong acid but a relatively flat line follows as the buffer is established. With the addition of more titrant, the graph passes the buffer region and an drop in pH level can once again be seen. The equivalence point is about the pH level of 5, which is due to the strong acid. The pH after this equivalence point is now dependent on the extra H3O+.

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3. Is the unknown a strong/weak acid/base? Explain your answer. The unknown is a strong acid. Based on the initial pH alone we can conclude that it is indeed a strong acid. And also in support to this the titration curve of the unknown shows the characteristic that of a strong acidstrong base titration theoretical titration curve upon comparison having that steep change in pH and with no buffering region. 4. Determine the concentration of the unknown sample. (MNaOH)(VNaOH) = (Mnitric acid) (Vnitric acid at eq. point) (0.1 M)(25mL) = x (25 mL nitric acid + 21.1 mL NaOH) x = 0.0542 M Conclusion The titration curve of strong acid-strong base starts from with a very low pH initially before reaching its equivalence point of 7, the pH gradually changes and is determined by the + remaining H3O . A change can be noticed when it reaches its equivalence point, in which the number of moles of the acid and the base are equal. After the equivalence point, the titration curves pH levels are determined by the excess OH-. In the case of weak acid-strong base and weak base-strong acid titration curves, initial pH are determined by the amount of the weak acid/base added. After this point, an abrupt change in pH level can be observed until the pH level for establishing a buffer region is reached, and the pH levels and the curve can be observed to have gradual changes. The pH before equivalence point can be determined by the amount of the acid/base and its conjugate base/acid. At equivalence point, the weak acidstrong base has a pH more than 7, while the weak base-strong acid has a pH less than seven. Both are determined by the hydrolysis of the cation and the anion of the salt formed. After equivalence point, the pH levels are due to the excess H3O+ or OH-. Recommendations As a recommendation from our group, We strongly suggest the addition of more pH meters available for use. We also encourage the use of a volumetric pipet as indicated in the manual. Lastly, be very precise and accurate in

determining the volume of titrant being added to the analyte for the whole graph depends on the readings you will be getting from this incremental additions. Be very careful and patient in titrating. References y General Chemistry. 5th Edition. (2005). Chang, R. y Chemistry: The Central Science. 8th Edition. (2000) Brown, Theodore L., Burnsten E., Lemay, H. Eugene Jr. y http://www.ausetute.com.au/titrcurv.html y http://www.chemguide.co.uk/physical/aci dbaseeqia/phcurves.html

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