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University of Bahrain College of Science Department of Chemistry 1st Semester 2013/2014

CHEMY241 Lab Report # 01

Name: Bisma Bashir Mohammad ID # 20094704 Date: September 25, 2013 Instructor: Dr. Fadheela Al-Salman

Aim:
To determine acid dissociation constant (ka) for weak acids and hydrolysis constant (kw) for different solutions of salts of weak acids and transition metal cations by pH meter.

Introduction:
Many theories have been proposed to explain the concept of acidic and basic properties of compounds such as Arrhenius theory, Theory of Solvent Systems, Bronsted-Lowery Theory, Lewis Theory, and so on. pH which is the negative log of H+ is one of such use which is used for the indication of the acidic or basic nature of the solution. The scale is constructed from 0-14 where 7 is the neutral and above is basic while below 7 indicates acidic nature (Christian, 2004). Here the strength of acidity of basicity can also be measured. Strong acids and bases are those which are completely ionized releasing the H+ and OH-. On the other hand, weak acids and bases are those which do not completely ionize. If a solution has its pH value near to 7 then it is a weak acid or base while solutions having pH far are stronger (Harris, 2007). For weak acids and bases, the extent of ionization is calculated by means of its acidity and basicity constants. It is expressed as Ka and Kb of the acid and base and is explained by the following equations: HA + H2O Ka = B + H2O Kb = Water containing both the H3O+ and OH- undergoes auto-ionization. The extent of auto-ionization is expressed as auto-ionization constant (kw). H2O H3O+ + OHKw = [H3O+] [OH-] Since pH of pure water is 7 i.e. neutral so it means [H3O+] = [OH-]. Experimentally it is found that [H3O+] = 1 mol/dm3 which means the kw value is the product of the two ions which will be equal to 1 mol/dm3 (Atkins et al., 2010). Hydrolysis of weak acid or base with water will yield anion of weak acid and cation of weak base which reacts with water anions and cations to react an equilibrium stage. Weak acid salts will result in basic solution while the weak base salts will turn the solution acidic. Hydrolysis constant of that solution can calculated by multiplying the ka of weak acid with kw of water (Lab manual, 2013). HB+ + OHA- + H3O+

Procedure:
Refer to lab manual.

Results and Calculations:


ka for weak acids is calculated as follows:

HA + H2O Ka =

A- + H3O+ =

Table 1: Acid Dissociation Constants of Weak acids Solutions pH 10-pH = [H3O+] 10-3.09 = 8.13 3.98 0.1 - [H3O+] = [HA] 0.1- 8.13 = 0.099 0.096 = Ka % error = 6.66 1.65 61.94% 87.86% = =

CH3COOH

3.09

ClCH2COOH 2.40

Kh for weak acids is calculated as follows: + H2O Kh = HA + OH=

Table 2: Hydrolysis constants of salts of weak acids Solutions pH [H3O+] 10-8.82 = 1.51 = [OH ] = 6.61 9.55 2.88 2.40
-

0.1 - [OH-] = [A-] 0.1 - 6.61 0.100 0.099 0.100 0.076

= Khexp = 4.37 9.21 8.32 7.57

= Khthe

% error 98.1%

NaHCO3

8.82

2.25 2.13 1.58 2.38 95.7% 94.7% 68.2%

Na2CO3 10.98 1.05 Na2HPO4 9.46 3.47 Na3PO4.12H2O 12.38 4.17

Kh for transition metal cations is calculated as follows: Mn+ + 2nH2O Kh = Table 3: Hydrolysis constants of Transition metal cations M(OH)n + nH3O+

Solutions NaCl

pH 7.01

[H3O+] 1 3.02 1

= [OH ] = 3.31 1.46 1.45 2.15


.
-

[Mn+] Khexp -

= Khthe -

% error 1.46 % 0% 0%

Cu(NO3)2.3H2O 3.52 SnCl2.2H2O FeCl3 1.92 2.09

= 9.12 1.00 2.50 6.25 1.00 2.50

1.20 8.13

8.32 1.23
and 4

Ksp= values for SnCl2.2H2O and FeCl3 are 1

Discussion:
Part 1: Here, acidity constants for weak acids were calculated. pH of Acetic acid and Chloroacetic acid were compared and then their ka values were obtained. According to table 1, Acetic acid had low pH value than the Chloroacetic acid. This is because of the replacement of H from Acetic acid to Cl of Chloroacetic acid. Chlorine being more electronegative will attract more electrons towards it in sharing and will weaken the bond between O and H in the acidic group. The weakened bond is more prone to cleavage and results in releasing of H+ in solution making it more acidic (Harris, 2007). Comparing the experimental values with the theoretical ones high percentage of errors was found in both i.e. 61.9% and 87.8% for Acetic acid and Chloroacetic acid respectively. There could be several reasons for this such as inappropriate handling of pH meter or any other personal error. The dissociation reactions of the solutions are as follows: CH3COOH + H2O ClCH2COOH + H2O CH3COO- + H3O+ ClCH2COO- + H3O+

Part 2: Kh values of aqueous solutions of several salts of weak acids were calculated by measuring their pH. pH of NaHCO3, Na2CO3, Na2HPO4 and Na3PO4.12H2O was found to be 8.82, 10.98, 9.46 and 12.38 respectively. Table 2 shows the detail steps of calculations. Here comparison is done between NaHCO3 and Na2CO3 i.e. pH of NaHCO3 is 8.82 less than that of Na2CO3 (10.98). According to theory, pH near to neutral are less basic therefore, NaHCO3 is mildly basic whereas Na2CO3 is strongly basic (Christian, 2007). The other two solutions i.e. Na2HPO4 and Na3PO4.12H2O also showed the same trend. Here Na2HPO4 was less basic and Na3PO4.12H2O was more. Hydrolysis constant of these salts explains the same thing that Na2CO3 and Na3PO4.12H2O are more soluble in water releasing more of the OH- making the solution basic than the NaHCO3 and Na2HPO4. Again, experimental values were compared with the theoretical ones and 98.1%, 95.7%, 94.7% and 68.2% errors were obtained. They are again high which means again some mistake was done while conducting the experiment. Another possible reason could be that instrument was not properly calibrated as same instrument was used in both parts. All the 3 solutions are basic due to the production of a strong base while reacting with water as shown below: NaHCO3 + H2O Na2CO3 + H2O H2CO3 + NaOH NaOH + HCO3-

Na2HPO4 + 2H2O 2NaOH + H3PO4 Na3PO4.12H2O + H2O 3NaOH + H3PO4 Part 3: Here, Kh values of transition metal cations were calculated indirectly by using pH meter. Table 3 shows the calculations done to calculate Kh from pH. Transition metal cations when dissolve in water yields acidic solution. pH of NaCl was measured as a reference for other since it has equal number of cations and anions. Here SnCl2.2H2O was found to be the strong acid solution due to low pH of 1.92 followed by FeCl3 of 2.09 and Cu(NO3)2.3H2O of 3.52. All the 3 solutions are acidic due to the production of strong acids while reacting with water as shown below: SnCl2 + 2H2O Sn(OH)2 + 2HCl 3Cu (NO3)2 + 3H2O 3CuO + 6HNO3 FeCl3 + 3H2O Fe(OH)3 + 3HCl

Calculating % errors in this part showed 0% error with Sn and Fe whereas Cu metal showed >100% error. Again this high percentage of error is mainly due to several personal and instrumental errors during the experimental setup. To avoid such inaccuracies, extra care should be taken during the process.

Conclusion:
In this lab, Ka values for weak acids, Kh for salts of weak acids and transition metal cations were performed with few errors.

References:
Atkins, P.W., Overton, T.L., Rourke, J.P., Weller, M.T. and Armstrong, F.A. (2010). Shriver and Atkins Inorganic Chemistry. 5th Eds, W. H. Freeman and Company, New York, U.S.A. Christian, G.D. (2004). Acid Base Equilibria In Analytical Chemistry. 6th Eds, John Wiley and Sons, INC., U.S.A. Harris, D.C. (2007). Monoprotic Acid Base Equilibria In Quantitative Chemical Analysis. 7th Eds, W. H. Freeman and Company, New York, U.S.A. Lab manual (2013). Inorganic Chemistry.