Experiment No. 8: Titration Curve Reyes, Juan Sebastian B., Tumimbang, Glenn Vincent L. Group 8, Chemistry 18.

1, CD-1, Prof. Arlou Angeles I. Abstract Titration is one of the experimental methods employed to determine the concentration of an analyte through the addition of a titrator or titrant of known concentration. Since volume is one of the key factors in the process, it is also referred to as volumetric analysis. In the earlier part of the experiment, where acid-base titrations of varied strengthsstrong acid vs. strong base, weak acid vs. strong base, strong acid vs. weak base are involved, the function of the pH of the analyte as increments of the titrant were added was observed through a graph called the titration curve. A titration curve is a graph showing the relationship of the pH changes as a volume of the titrant was added. Four titration curves were made: one for HOAc and NaOH, HCl and NaOH, NH4OH and HCl, and NaOH and HCl as the analyte and titrant, respectively. The latter part of the experiment, involving the titration curve of an unknown, was not performed. A pH meter was used to accurately measure the + pH, or changes in the [H3O ]. II. Keywords. Titration, Titration curve, Equivalence point, analyte, titrant III. Introduction In Chemistry, titration is one of the most common methods observed to determine the concentration of an unknown through the addition of a solution of a known concentration. The former is referred to as the analyte while the latter is the titrant. Although there are several types of titrations done, the reaction between an acid and a base is used to evaluate the concentration needed, acidbase titrations were used in this experiment. With varying strengths, a graph called a titration curve can be made to show the change and relationship in the pH of the unknown in the addition of the titrant, necessary for the aimed results. In a titration curve, several key points are observed. The equivalence point, also known as the stoichiometric point, is a point where the titrant is stoichiometrically equal to the number of moles of the analyte. In a strong acid-strong base titration, the equivalence point is the point of neutralization + where the pH accounts to the [H ] and [OH ] of the reaction equal to that of water, 7. In a strong acidweak base or weak acid-strong base titrations, the equivalence point is the point where the minimum amount of titrant needed to neutralize the analyte is determined, thus employing the method of finding the limiting reactant. In these cases, the pH will not be equal to that of water, and instead, will closely depend on the acidity or basicity strengths involved in the reaction. The end point, more observed in the presence of an indicator, is reached when a color change signals that the analyte has been neutralized. A buffer region can also be observed in the titration curve between a weak electrolyte and a strong one. This area is where the maximum amount of hydroxide or hydronium ions are held by the buffer, supressing the abrupt change in pH. It can be seen as a nearly straight horizontal line. It can also be seen that it is followed by an abrupt change in the pH, more seen as a nearly straight horizontal line, signalling that the buffer can no longer supress the changes that occurs. IV. Experimental Part A. Preparation of Standard Titration Curves Using a pH meter to accurately measure the initial pH of a 25-mL 0.1 M HOAc, increments of 2 mL of the titrant, 0.1 M NaOH, was added. The pH was recorded after each addition. When an abrupt change in pH is observed, the increments were halved until the reading reaches close to12 for acid-base titrations while 2 for base-acid ones. The same methods were done using 0.1 M HCl with 0.1 M NaOH and 0.1 M NH4OH with 0.1 M HCl. Also, to substitute the analysis of the unknown solution, 0.1 M NaOH was made as an analyte while 0.1 M HCl became the titrant, opposite to the second set. V. Results Part A. Preparation of Standard Titration Curves Set I. Titration of 25 mL of 0.1 M HOAc with 0.1 M NaOH
Table 1. Titration of 25 m L 0.1 M HOAc w ith 0.1 M NaOH

Volume (mL) 0

pH reading 2.37

Chemistry 18.1, Titration Curve

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pH

2 4 6 8 10 12 14 16 18 20 22 24 25 26 27 28 29 30 31 32 33 34

3.61 3.92 4.14 4.33 4.49 4.64 4.80 4.97 5.17 5.44 5.93 9.82 11.23 11.44 11.56 11.65 11.71 11.77 11.81 11.84 11.87 11.90

18 19 20 21 22 23 24 25 26 27 28 29

11.64 11.68 11.69 11.77 11.79 11.85 11.85 11.85 11.92 11.94 11.94 12.00

Graph 2. Titration Curve of HCl w ith NaOH

14
12 10 8 6

Graph 1. Titration Curve of HOAc w ith NaOH

14
12

4
2 0 0 10 20 30 40

10
pH 8

Volume (mL)

6
4

2
0

10

20 Volume (mL)

30

40

Set III. Titration of 25 mL of 0.1 M NH4OH with 0.1 M HCl

Table 3. Titration of 25 m L 0.1 M NH4OH w ith 0.1 M HCl

Volume (mL) Set II. Titration of 25 mL of 0.1 M HCl with 0.1 M NaOH
Table 2. Titration of 25 m L 0.1 M HCl w ith 0.1 M NaOH

pH reading 10.20 9.34 8.72 6.53 2.28 2.19 2.14 2.06 2.03 2.02 2.01 2.00

Volume (mL) 0 2 4 6 8 10 12 14 16

pH reading 2.07 2.08 2.09 2.10 2.14 2.22 2.32 2.49 3.20

0 2 4 6 8 9 10 11 12 12.5 13 13.5

Chemistry 18.1, Titration Curve

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14
12
Graph 3. Titration Curve of HOAc w ith NaOH

10

12

10
8 pH 6

pH

8 6

4
2

4
2 0

0
0 5 10 15 20 25 Volume (mL)

10

15

V. Discussion Part A. Preparation of Standard Titration Curves For the experiment, we constructed four titration curves of different reactions involving acids and bases of varying strengths. The independent variable is the volume in millilitres while the dependent variable is the pH, as what is shown by its change when the volume is increased. Basically, a titration curve would show the change in pH of the analyte as the titrant is added. There are three types of this curve; one for a strong acid and a strong base, another for a weak acid and strong base, and finally for a strong acid and weak base. Each of these may vary in appearance in the graph, and this is due to the differences in the initial pH, the magnitude of the equivalence point, and the strengths of the acids and bases involved. Generally, the titrant used is always of high strength for the graph to emphasize the changes that will occur. Use of a weak titrant against a weak analyte would have a very long and slow reaction which is not feasible for the graph. A titration curve between an acid and base generally has three parts: the region before the equivalence point, or the pre-equivalence point; the point when the number of moles of the titrant is, ideally, equal to that of the analyte, or the equivalence point; and the region after the equivalence point, post-equivalent. But this is not true for all titrations. The reason is, as stated above, the difference in the strength of electrolytes. In the first set where 0.1 M HOAc, a weak acid and the analyte, is reacted to 0.1 M NaOH, a strong base and the titrant, the graph starts below 7, showing the acidity of the analyte. But as millilitres of the titrant were added, the pH started to increase up to a point where the solution is basic.

Volume (mL)

Set IV. Titration of 15 mL of 0.1 M NaOH with 0.1 M HCl

Table 4. Titration of 25 m L 0.1 M NaOH w ith 0.1 M HCl

Volume (mL) 0 2 4 6 8 10 12 13 14 15 16 17 18 19 20 21

pH reading 11.85 11.85 11.79 11.77 11.69 11.68 11.64 3.20 2.49 2.32 2.22 2.14 2.10 2.09 2.08 2.07

Graph 4. Titration Curve of HCl w ith NaOH

Chemistry 18.1, Titration Curve

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CH3COOH + NaOH

NaCH3COO + H2O

A. 25 mL 0.1 M HOAc with 0.1 M NaOH HOAc + NaOH HOAc + OH a.

-

Since NaOH is a strong base, it is therefore a strong electrolyte. As a result, it completely + dissociates into the Na and OH ions. For that reason, we can write the equation as: CH3COOH + Na + OH
+ -

NaOAc + H2O OAc + H2O

-

Na + CH3COO + H2O HOAc + H2O OAc

0 mL NaOH, initial pH
-

+ H3O

Now that the equation has become like this, + we can remove the Na ion since it appears in both reactant and product side and does not affect the pH much than the acetate. Doing that, we get: CH3COOH + OH
-

i c e

0.1M -x 0.1M -x
-5

0 +x x

0 +x x

CH3COO + H2O

Analyzing the equation above, it is obvious that the reaction led to the formation of acetate, the conjugate base of acetic acid. This satisfies the requirements to form a buffer solution. It is due to this reason that there was an observed buffered region before the equivalence point. But, the equivalence point of a weak acid/base-strong acid/base is not equal to 7. The presence of a salt produced by the reaction greatly affects the pH of the solution. And thus, a weak acid -strong base will yield an equivalence point with a pH greater than 7, while a weak base -strong acid will yield an equivalence point with a pH less than 7. This also applies similarly to the reaction between NH4OH, a weak base and the analyte, to a stronger electrolyte, HCl as the titrant. The difference can be observed from the starting point because of its basicity, and eventually leading to an equivalence point where the pH is greater than 7. The magnitude of this point is also closely similar to that of the first set, showing the relationship between a weak base and strong acid similarly to the reaction between a strong base and a weak acid. As for the reaction between HCl and NaOH, both strong electrolytes, the equivalence point is shown to be of greater magnitude than the other two involving a weaker electrolyte and a strong one. This is due to the abrupt change in the pH, and the + complete dissociation of both [H3O ] and [OH ], having the two mentioned electrolytes in the same molarity and volume, in the solution accounts for the pH that is nearly equal to or equal to 7. VI. Guide Questions 1. Construct the titration curve of the following, in increments of 5 mL.

Ka = 1.8x10 + Ka = [H3O ] [OAc ] [HOAc] + [H3O ] = [OAc ] [H3O ] = [

+

pH

= ( -3 = 1.34 x 10 M + = -log [H3O ] -3 = -log [1.34x10 ] = 2.87 b. 5 mL NaOH HOAc + OH

i c e 2.5 mmoles -0.5 mmoles 2.0 mmoles
-

] ) (

OAc + H2O
0.5 mmoles -0.5 mmoles 0
-5

0 +0.5 mmoles 0.5 mmoles

pKa = -log Ka = -log 1.8x10 = 4.74

] [ ]

c.
i c e

10 mL NaOH HOAc
2.5 mmoles -1.0 mmoles 1.5 mmoles
-5

OH

OAc + H2O
0 +1.0 mmoles 1.0 mmoles -

1.0 mmoles -1.0 mmoles 0

pKa = -log Ka = -log 1.8x10 = 4.74

] [ ]

d.

15 mL NaOH

Chemistry 18.1, Titration Curve

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HOAc + OH
i c e 2.5 mmoles -1.5 mmoles 1.0 mmoles

OAc + H2O
1.5 mmoles -1.5 mmoles 0 0 +1.5 mmoles 1.5 mmoles -

[ (

] )

[ [ ]

B. 25mL 0.1 M HCl with 0.1M NaOH HCl + NaOH + H3o + OH HCl + H2O NaCl + H2O H2O + Cl + H3O

e.

20 mL NaOH HOAc + OH
i c e 2.5 mmoles -2.0 mmoles 0.5 mmoles
-

OAc + H2O
2.0 mmoles -2.0 mmoles 0 0 +2.0 mmoles 2.0 mmoles -

[ [ ]

a. 0 mL NaOH, initial pH + [H3O ] = Vanaly teManaly te - Vtitrant Mtitrant Vsolution = [(25 mL)(1 M)] [(0)(1 M)] 50 mL = 0.1 pH = - log[0.1] =1 b. 5 mL NaOH + [H3O ] = Vanaly teManaly te - Vtitrant Mtitrant Vsolution = [(25 mL)(1 M)] [(5 mL)(1 M)] 50mL + 5mL = 0.082 pH = - log[0.082] = 1.09

f.

25 mL NaOH, equivalence point HOAc + OH

i c e 2.5 mmoles -2.5 mmoles 0
-

OAc + H2O
0 +2.5 mmoles 2.0 mmoles -

2.5 mmoles -2.5 mmoles 0

OAci c e 0.05 M -x 0

+ H2O
-

HOAc + OH0 +x x 0 +x x

c. 10 mL NaOH + [H3O ] = Vanaly teManaly te - Vtitrant Mtitrant Vsolution = [(25 mL)(1 M)] [(10 mL)(1 M)] 50 mL + 10 mL = 0.067 pH = - log[0.067] = 1.17 d. 15 mL NaOH + [H3O ] = Vanaly teManaly te - Vtitrant Mtitrant Vsolution = [(25 mL)(1 M)] [(15 mL)(1 M)] 50mL + 15mL = 0.067 pH = - log[0.067] = 1.17 e. 20 mL NaOH + [H3O ] = Vanaly teManaly te - Vtitrant Mtitrant Vsolution = [(25 mL)(1 M)] [(20 mL)(1 M)] 50 mL + 20 mL = 0.043 pH = - log[0.043] = 1.37

Kb = [OH] [HOAc] / [OAc] -10 2 5.6 x10 = x / 0.05-x -6 x = 5.27 x 10 pOH pH = -log (5.27 x 10 = 14-5.28 = 8.72 30 mL NaOH HOAc + OH
i c e 2.5 mmoles -2.5 mmoles 0
-6

pOH=5.28

g.

OAc + H2O
0 +2.5 mmoles 2.0 mmoles -

3.0 mmoles -2.5 mmoles 0.5 mmoles

Chemistry 18.1, Titration Curve

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[
f. 25 mL NaOH, equivalence point + [H3O ] = Vanaly teManaly te - Vtitrant Mtitrant Vsolution = [(25 mL)(1 M)] [(25 mL)(1 M)] 50 mL + 20 mL =0 + pH = - log[H2O], neutralization, [H3O ][OH ] =7

] [ ]

c.

10 mL HCl NH4OH + H3O

+

NH3 + H2O
0 +1.0 mmoles 1.0 mmoles -

g. [OH ]

pOH = = pH = =

30 mL NaOH = Vanaly teManaly te - Vtitrant Mtitrant Vsolution = [(50 mL)(1 M)] [(30 mL)(1 M)] 50 mL + 30 mL = 0.025 - log[0.025] 1.60 14 pOH 12.24

i c e

2.5 mmoles -1.0 mmoles 1.5 mmoles

1.0 mmoles -1.0 mmoles 0

-5

pKa = -log Ka = -log 1.8x10 = 4.74

] [ ]

C. 25 mL 0.1 M NH4OH with 0.1 M HCl d. NH4OH + HCl NH4OH + H3O a.

+

15 mL HCl NH4OH + H3O

+

NH3Cl + H2O
+ NH3

NH3 + H2O
0 +1.5 mmoles 1.5 mmoles -

+ H2O

i c e
-

2.5 mmoles -1.5 mmoles 1.0 mmoles

1.5 mmoles -1.5 mmoles 0

0 mL HCl, initial pH NH4OH + H2O NH3

+

+ OH

I C E

0.1M -x 0.1M -x
-10

0 +x x

0 +x X

[ [ ]

Kb = 5.6 x 10 + Kb = [NH3 ] [OH ] [NH4OH] + [OH ] = [NH3 ] [OH ]

-

= [

] )

e.

20 mL NaOH NH4OH + H3O

i c e 2.5 mmoles -2.0 mmoles 0.5 mmoles
+

pH

= ( ) ( -6 = 7.45 x 10 M = -log [OH ] -6 = -log [7.45x10 ] = 11,13 b. 5 mL HCl NH4OH + H3O

i c e 2.5 mmoles -0.5 mmoles 2.0 mmoles
+

NH3 + H2O
0 +2.0 mmoles 2.0 mmoles -

2.0 mmoles -2.0 mmoles 0

[ [
+ NH3

] ]

+ H2O
0 -

0.5 mmoles -0.5 mmoles 0

-5

+0.5 mmoles 0.5 mmoles

pKa = -log Ka = -log 1.8x10 = 4.74 pKb = 9.25

f.

25 mL HCl, equivalence point

Chemistry 18.1, Titration Curve

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NH4OH + H3O
i c e 2.5 mmoles -2.5 mmoles 0

NH3 + H2O
0 +2.5 mmoles 2.0 mmoles -

VII. Conclusion and Recommendations There are key points that should be observed in a titration curve. The most important one is the equivalence point which shows the neutralization of the analyte. This also emphasizes the different titration curves that will be formed with varying strengths of the electrolytes to react with one another. It can also be concluded that the titration between two strong electrolytes would yield a pH that is equal to 7 at equivalence point due to the complete dissociation of the ions for neutralization. On the other hand, the pH of a strong acid-weak base titration would be close but less than 7 while the pH of a weak acid-strong base titration would be close but greater than 7. This is accounted by the partial dissociation of the electrolytes, whichever is the weaker one. The graph also shows a difference in the magnitude at the equivalence point; larger in two strong electrolytes and shorter in weak electrolyte as the analyte. For the experiment, we recommend to use fewer increments to actually have a complete and accurate on the changes on the pH as the process goes on. This will show a better understanding of the equivalence point and titration as a whole. VIII. References Brown, Theodore and LeMay, H.E. (2009) Chemistry: The central science. Pearson Education Inc. Jurong, Singapore. Chemistry Tutorial: Acid-Base Titration Curves Retrieved on 16, March 2011 from http://www.ausetute.com.au/titrcurv.html

2.5 mmoles -2.5 mmoles 0

NH3+ + H2O
i c e 0.05 M -x 0.05-x +

NH4OH + H3O+
0 +x X 0 +x x

Ka = [H3O] [NH4OH] / [NH3 ] -5 2 1.8 x10 = x / 0.05-x -6 x = 5.27 x 10 pH pH = -log (5.27 x 10 ) = 14 - 8.72 = 5.28 g. 30 mL HCl NH4OH + H3O
i c e 2.5 mmoles -2.5 mmoles 0
+ -6

pH=8.72

NH3 + H2O
0 +2.5 mmoles 2.0 mmoles -

3.0 mmoles -2.5 mmoles 0.5 mmoles

[ (

] )

2. Discuss the results in Part A. The titration curves shown in the first part of the experiment vary due to the differences in the strengths of the acids and bases involved. In the first set, the titration between HOAc and NaOH, a weak acid and strong base, respectively, shows less magnitude at the equivalence point. This is due to the partial dissociation of the weaker electrolyte to the stronger one. Generally, the titration curve between a weak electrolyte as the analyte and a titrant shows that the pH at the equivalence point is either greater than or less than 7. For strong acidweak base titrations, it accounts to a pH below that of water while the other way around in weak basestrong acid titrations. On the other hand, the titration curves shown by the reaction between two strong electrolytes have a higher and longer magnitude in the equivalence point. As what the complete + dissociation of the electrolyte shows, the [H3O ] and [OH ] would account to the pH that is equal to that of water.

I hereby certify that I have given substantial contribution to report.

Reyes, Juan Sebastian B.

Tumimbang, Glenn Vincent L.

Chemistry 18.1, Titration Curve

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