Common-Ion Effect and Buffers

Shela Marie L. Algodon National Institute of Molecular Biology and Biotechnology, University of the Philippines, Diliman, Quezon City 1101 Philippines Experimental Details Four different volumes of the following solutions were prepared in separate 50-mL beakers: Solution 1: 30 mL 0.10 M HOAc Solution 2: 15 mL 0.20 M HOAc 15 mL 0.20 M NaOAc Solution 3: 30 mL 0.10 M NH3 Solution 4: 15 mL 0.20 M NH3 15 mL 0.20 M NH4Cl The pH of each solution was estimated using indicators. One drop of methyl orange served as indicator for Solutions 1 and 2. The colors of the two solutions were compared afterwards. On the other hand, one drop of phenolphthalein indicator was used as an indicator for Solutions 3 and 4. The colors of the solutions were also compared. Using a properly calibrated pH meter, a more accurate pH reading of each solution was obtained. After determining the pH of each solution using a pH meter, each solution was divided into three equal portions. One drop of 1.0 M HCl was added to the first portion. To the second portion, one drop of 1.0 M NaOH solution was added. The third portion served as the control and the colors of the other two portions were compared with it. Again, the pH of each solution was estimated based on their colors, and a more accurate pH was obtained using the pH meter. The effect of common ions on the solutions and the effect of adding other reactants in a buffer solution in this experiment are thus observed. Results and Discussion Report A buffer solution is a solution consisting of a conjugate acidbase pair where both the concentrations of the acid and the base are reasonable. Buffer systems resist changes in the pH upon addition of small amounts of strong acid or strong base. The acid in the buffer solution reacts with the strong bases added in the solution. Similarly, the base in the buffer solution reacts with the strong acids added in the solution2. One factor affecting the processes involved in the buffer solution is the common ion effect, a special case of LeChateliers Principle. Many solutions exhibit this kind of behaviour. However, the most frequently encountered types of solutions are (1) a solution of a weak acid plus a soluble ionic salt of the weak acid and (2) a solution of a weak base plus a soluble ionic salt of the weak base1, 3. TABLE 1: pH Using Visual Indicators and pH Meter Color of Solution Solution + Methyl Orange Salmon pink Yellow Red Very light pink + Phenolphthalein pH Reading

1 2 3 4

3.34 4.82 10.02 8.85

TABLE 2: Effect of Strong Acid and Strong Base on Buffers Estimated pH Range Soluti on + Meth yl Oran ge No chan ge Light er salm on pink Norm al No chan ge No chan ge Norm al Very light pink Light pink Normal Lighter than normal No change Normal + Phenolphtha lein pH Met er pH Calcula ted

a 1 b

3.28

2.27

3.52

3.47

to the first portion, 1 drop 1.0 M NaOH was added to the second portion, and the third portion served as the control solution, there were changes in the pH of the first two portions. It is because there is initial concentration for the H+ ion in portion 1, Solution 1a. This initial concentration attributes to the extent the forward reaction will proceed, as had been stated in the LeChateliers Principle. The reason is the same for Solution 1b, the portion with 1 drop of 1.0 M NaOH. Because the NaOH dissociates into Na+ and OH- ions completely, the OH- ions react with the CH3COOH to form CH3COO- and H2O, giving the CH3COO- an initial concentration before the dissociation of the CH3COOH alone. The pH of Solution 2, the solution with 15 mL 0.20 M CH3COOH and 15 mL 0.20 M NaCH3COO, has a different pH from Solution 1 even if the solution also has the same concentration of CH3COOH because CH3COO-, the common ion, has an initial concentration. This solution is a buffer solution. The NaCH3COO, a soluble ionic salt of CH3COOH, completely dissociates into Na+ and CH3COO-. On the other hand, CH3COOH only partially ionizes. When it was divided into three portions, the same reaction as that of Solution 1a and Solution 1b happens with the Solution 2a and 2b. Since there is a common ion CH3COO-, the change in the pH of the solution will be minimal compared to Solutions 1a and 1b since CH3COO- will react with the added strong acid, and CH3COOH will react with the added strong base. The same principle applies for both Solutions 3 and 4 and their portions. The pH of the solution with 30 mL 0.10 M NH3, Solution 3, was obtained by calculating the amount of OH- ions and using the equation for pOH: pOH=-log[OH-]. Since pH is what is asked, the value for pOH is subtracted from 14 based on the formula pH + pOH=14. The solution is divided into three portions. When 1 drop of 1.0 2

c a 2 b

3.34 4.43

2.86 4.70

4.79

4.79

c a 3 b c a 4 b c

4.82 9.33 9.77 10.0 2 8.25 8.63 8.85

4.74 10.53 11.73 11.12 9.23 9.30 9.26

In Solution 1, the solution with 30 ml of 0.10 M CH3COOH, the pH was obtained just by getting the concentration of the H+ ion in the solution and the formula for pH: pH=-log[H+]. When the solution was divided into three equal portions, where 1 drop of 1.0 M HCl was added

M HCl was added to the first portion, the H+ from the completely dissociating HCl reacts with NH3 to form NH4+. Thus, there is an initial concentration for NH4+. On the other hand, when NaOH was added to the second portion, the NaOH dissociates completely into Na+ and OH-, giving an initial concentration of OH- ions even before NH3 dissociates. When the HCl and NaOH was added to solution 4, the solution with 15 mL 0.20 M NH3 and 15 mL 0.20 M NH4Cl, there is not much change in the pH since it is a buffer solution. Strong acids and strong bases react with the existing bases and acids, respectively, as is the case for this solution. The H+ ions from the added HCl reacts with the NH3 producing more NH4+ in return. Similarly, the OH- ions from the added NaOH reacts with NH4+ to produce the compound NH3. As can be seen from Table 2, the values obtained from using a pH meter to determine the pH of the solution is different from the values theoretical values obtained. This is in account for the human errors and the accuracy of the

measuring equipment which doesnt always give exact amounts. However, it should be noted that the trend in changes of the pH for both the experiment and theoretical values of the pH are the same. It is recommended to use more accurate measuring devices so as to get more reliable data, and avoid errors. Moreover, it should always be remembered to wait for the stable sign in the pH meter before recording data.

References (1) Ebbing, D. D., Gammon, S. D.(2009) General Chemistry, 9th ed. USA: Houghton Mifflin Company (2) Pauling, L. (1970) General Chemistry. US: Dover Publications (3) Whitten, K. W., et al. (2004) General Chemistry, 7th ed. US: Brooks/Cole

Appendices Appendix A pH of Solution 1: 30 mL 0.10 M HOAc

CH 3COOH
Initial Change Equilibrium 0.10 x 0.10 - x

CH 3COO 
0 +x x

H
0 +x x

CH 3COO  H  Ka ! CH 3COOH A ? 1.8 v 105 !

x x 0.10  x

x ! 1.332670973 v 103

pH !  log H  pH !  log 1.332670973 v 103 pH ! 2.875277062

Appendix B pH of Solution 2: 15 mL 0.20 M HOAc 15 mL 0.20 M NaOAc

?baseA pH ! pK a  log ?acid A ?0.20A pH !  log(1.8 v10 5 )  log ?0.20A pH ! 4.744727495

Appendix C pH of Solution 3: 30 mL 0.10 M NH3

NH 3
Initial Change Equilibrium 0.10 x 0.10 x

H 2O

p n

 NH 4

OH 
0 +x X

0 +x x

 NH 4 OH  Kb ! NH 3 A ?

1.8 v 105 !

x x 0.10  x

x ! 1.332670973 v 103

pOH !  log OH  pOH !  log 1.332670973 v10 3 pOH ! 2.875277062

pH  pOH ! 14 pH  2.875277062 ! 14 pH ! 11.12472294

Appendix D pH of Solution 4: 15 mL 0.20 M NH3 15 mL 0.20 M NH4Cl

?acid A pOH ! pK b  log ?baseA ?0.20A pOH !  log(1.8 v10 5 )  log ?0.20A pOH ! 4.744727495

pH  pOH ! 14 pH  4.744727495 ! 14 pH ! 9.255272505