EXPERIMENT 1 Determination of Ka of Acetic Acid From Conductance Measurements Introduction Dissociation is the term used to describe the breakdown

of a molecule into simpler parts. The equilibrium constant for such a reaction is called dissociation constant. The dissociation constant of a compound is important for a number of reasons: 1) The dissociation constant of a compound can help us determine the environmental impact of a chemical. 2) The dissociation constant can also help us to determine the biological impact of a chemical. 3) Dissociation constants are also useful in helping us to calculate the pH of a weak acid or base. When an acid reacts with water it dissociates into its conjugate base and a single proton which attaches to a water molecule forming hydronium ion. Some acids, like HCl, are strong acids and dissociate completely, meaning that virtually every HCl reacts with water to produce H3O+ and Cl- ions. Other acids, like acetic acid, are considered weak and only dissociate partially. The degree to which they dissociate is represented by the acid dissociation constant, Ka. The larger the value of Ka, the more the acid dissociates, and vice versa. There are a number of ways that dissociation constants can be calculated. One technique that you may be the most familiar with is the use of a pH meter to determine the dissociation constant of an acid or base (Ka or Kb) in water by conducting a titration. Another method uses a spectrophotometer to determine the concentrations of ionized and unionized forms based on their absorbance spectra. A third way to determine dissociation constants is by measuring the conductivity of a solution at varying concentrations. In this exploration, you will be utilizing this third method. For a solution to carry a current there must be charged species present that are able to move from one place to another. The measurement of that ability to carry a current is called conductance. The conductance of current in solution obeys Ohms Law Where I = the current in amperes, V = the potential in volts, and R = the resistance in ohms. The resistance of any conductors varies directly with its length l and inversely with its cross-sectional area, A, according to the equation The proportionality constant is known as the specific resistivity whose value depends on the nature of the conductor. It has the unit ohmcm. The conductance L, expressed in ohm-1, is the reciprocal of the resistance. Thus we have [ ][ ]

The molar conductance , on the other hand, is defined as the conductance of a volume of solution containing one mole of electrolyte when placed between two parallel electrodes one centimetre apart.

If the molar conductance of a strong electrolyte is plotted against c, a linear plot is obtained. The intercept at c = 0 is the limiting molar conductance. According to the Kohlrauschs Law of independent migration of ions, the limiting molar conductance may be defined as The immediate practical application of Kohlrauschs Law is the calculation of the limiting molar conductance of a weak electrolyte such as acetic acid. Alternaively, The evaluation of the degree of ionization of a weak electrolyte is based on the Arrhenius relation

The ionization constant Ka for a weak monoprotic acid can be expressed as ( which may be written as ( If is much greater than , then ) )

Objective To evaluate the apparent ionization constant of acetic from conductance measurements.

Schematic Diagram Prepare 250ml of standard solution of 0.02M KCl, 1M HOAc, 1M NaCl, 1M NaOAc and 1M HCl.

From 1M prepared solution, make 250ml 0f 0.10M, 0.08M, 0.06M, 0.04M and 0.02M of each electrolytes.

Standardized 0.02M of HCl and HOAc using standardized 0.05M NaOH.

Determine the conductance of each solutions prepared using conductivity bridge.

Data Determination of Cell Constant LKCl = 30.07 x 10-3 -1 Ls = 2.768 x 10-3 -1cm-1 Ldistilled water = 0.00 -1 Cell constant, K = 10.86 cm Table 1. Standardization of 0.0500M NaOH using KHP (KHC8H4O4) Trial Mass of KHP used Volume of NaOH consumed 1 0.1000 g 10.2 ml 2 0.1400 g 14.7 ml Average

Concentration of NaOH 0.04801 M 0.04664 M 0.04733 M

Table 2. Raw Data Taken after Titration of 1.000 M Acetic Acid using 0.17703 M NaOH Trial Volume of HOAc used Volume of NaOH consumed Concentration of HOAc 1 2 ml 11 ml 0.9737 M 2 2 ml 11 ml 0.9737 M Average 0.9737 M Table 3. Raw Data Taken after Titration of 0.0200 M Acetic Acid using 0.04733 M NaOH Trial Volume of HOAc used Volume of NaOH consumed Concentration of HOAc 1 10 ml 4.2 ml 0.01988 M 2 10 ml 4.3 ml 0.02035 M Average 0.020115 M Table 4. Raw Data Taken after Titration of 1.000 M Hydrochloric Acid using 0.17703 M NaOH Trial Volume of HCl used Volume of NaOH consumed Concentration of HCl 1 2 ml 10.9 ml 0.9648 M 2 2 ml 11.5 ml 1.018 M Average 0.9914 M Table 5. Raw Data Taken after Titration of 0.0200 M Hydrochloric Acid using 0.04733 M NaOH Trial Volume of HCl used Volume of NaOH consumed Concentration of HCl 1 10 ml 3.7 ml 0.01751 M 2 10 ml 4.5 ml 0.02130 M 3 10 ml 4.5 ml 0.02130 M Average 0.020004 M

Table 6. Conductance of solution with different concentration Concentration Conductance, L (ohm-1) (mol/L) CH3COOH HCl NaCl 0.02 0.000229 0.0110 0.00378 0.04 0.000379 0.0216 0.00748 0.06 0.000430 0.0304 0.0110 0.08 0.000483 0.0393 0.0130 0.10 0.000517 0.0467 0.0155 Table 7. Specific conductance of each solution with different concentration Concentration Specific Conductance, L (ohm-1cm-1) (mol/L) CH3COOH HCl NaCl 0.02 0.0000211 0.00101 0.000348 0.04 0.0000349 0.00199 0.000689 0.06 0.0000396 0.00280 0.00101 0.08 0.0000445 0.00362 0.00120 0.10 0.0000476 0.00430 0.00143

NaOAc 0.00222 0.00408 0.00580 0.00741 0.00898

NaOAc 0.000204 0.000376 0.000534 0.000682 0.000827

Table 8. Molar conductivity of four electrolytes Concentration C1/2 Molar Conductance, (-1cm2mol-1) 3 3 1/2 (mol/cm ) (mol/cm ) CH3COOH HCl NaCl NaOAc 0.00002 0.00447 1.055 50.50 17.40 10.20 0.00004 0.00632 0.8725 49.75 17.23 9.400 0.00006 0.00775 0.6600 46.67 16.83 8.900 0.00008 0.00894 0.5563 45.25 15.00 8.520 0.00010 0.0100 0.4760 43.00 14.30 8.270 Figure 1. Plot of versus for HCl solutions

Plot of versus c of HCl

Molar Conductance (-1cm2mol1)
52 50 48 46 44 42 0 y = -1395.2x + 57.492 R = 0.9468 0.005 c (in 0.01 mol/cm3) 0.015 HCl values Linear (HCl values)

Figure 2. Plot of versus

for the NaCl solutions

Plot of versus c of NaCl

Molar Conductance (-1cm2mol-1) 20 15 10 5 0 0 0.005 0.01 0.015 c (in mol/cm3) y = -589.31x + 20.569 R = 0.8296 NaCl values Linear (NaCl values)

Figure 3. Plot of versus

for the NaOAc solutions

Plot of versus c of NaOAc

Molar Conductance (-1cm2mol-1) 12 10 8 6 4 2 0 0 0.005 0.01 0.015 c (in mol/cm3) y = -350.65x + 11.686 R = 0.9892 NaOAc values Linear (NaOAc values)

Figure 4. Plot of (1/) versus c for the HOAc solutions

1/ of Acetic Acid with c

2.5 2 1/ 1.5 1 0.5 0 0 0.01 0.02 c 0.03 0.04 0.05 Series1 Linear (Series1) y = 40.207x + 0.0544 R = 0.9459

Sample Calculations Determination of cell constant

Determination of specific conductance of each solution with different concentration

Determination of molar conductivity of four electrolytes

Determination of and Ka for HOAc using Figure 1, Figure 2 and Figure 3 ( )

( ( Relative Error, ( ) )

Determination of and Ka for HOAc using Figure 4

( Relative Error, ( )

Discussion

The molar conductivity is found to vary according to the concentration. One reason for this variation is the number of ions in the solution might not be proportional to the concentration of the electrolyte. For instance, the concentration of ions in a solution of a weak acid depends on the concentration of the acid in a complicated way, and doubling the concentration of the acid added does not double the number of ions. Secondly, because ions interact strongly with one another, the conductivity of a solution is not exactly proportional to the number of ions present. The concentration dependence of molar conductivities indicates that there are two classes of electrolyte. The characteristic of a strong electrolyte is that its molar conductivity depends only slightly on the molar concentration. The strong electrolytes used in this experiment were HCl, NaCl and NaOAc. The characteristic of a weak electrolyte is that its molar conductivity is normal at concentrations close to zero, but falls sharply to low values as the concentration increases. Acetic acid was an example of weak electrolyte. The solution conducts electricity through motion of the ions under the effect of an electric field. At high concentrations, each ion is surrounded by other ions, both positive and negative. The field affecting any particular ion changes slightly because of these surrounding ions. At infinite dilution, the distance between nearest neighbor ions is large, and only the effect of the applied electric field is felt by individual ions. This is the reason for extrapolating the data to infinite dilution. The conductivity of any particular ion will also be affected by the ease with which the ion can more through the water. Hence different ions should contribute differently to the total measured conductivity. The ease with which any ion moves through the solution depends on considerations such as the total charge and the size of the ion; large ions offer greater resistance to motion through the water than small ions. In this experiment, the Ka for acetic acid was determined by measuring the conductivity of a solution at varying concentrations. The conductance of acetic acid varies from 229 siemens to 517siemens. The conductance of HCl ranges from 11.0 millisiemens to 46.7 millisiemens. The conductance of NaCl varies from 3.78 millisiemens to 15.5 millisiemens. Lastly, the conductance of NaOAc ranges from 2.22 millisiemens to 8.98 millisiemens. From the conductance of different solutions used, hydrochloric acid gave the largest value of conductance while acetic acid presented the smallest value. The cell constant used in the calculation of specific conductance of four different solutions was 10.86 centimeter. The cell constant was obtained from the conductance (30.07 millisiemens) and specific conductance (2.768 millisiemens/cm) of KCl. The calculated Ka value for acetic acid using the graphs of NaCl, HCl and NaOAc was while the limiting molar conductance was . On the other hand, the computed Ka value for acetic acid using the data of the conductance of the weak electrolyte was while the limiting molar conductivity was .

Conclusion

The dissociation constant of acetic acid is dependent on the temperature of the solution. Thus, increasing the temperature could also increase the Ka of the solution. In this experiment, the conductance of the solution was measured at the temperature of 300K to 311K. The calculated Ka of acetic acid in this experiment using the strong electrolytes molar conductivity was . It yields a relative error of 26.34%. The theoretical value -5 used was 1.75 x 10 M. The limiting molar conductivity of acetic acid was calculated to be . The true value for molar conductivity was set to be . Thus, the relative error was -24.48%. The negative sign indicated that the experimental value was larger than the true value. In contrast, the calculated Ka value for acetic acid using the data of the conductance of the weak electrolyte was while the limiting molar conductivity was . The percentage relative error was large. References T. Shedlovsky, Physical Methods of Organic Chemistry, edited by A. Weissberger, Volume 1, Chap XXV. Interscience Publishers, New York. Shoemaker, David P., Garland, Carl W. and Nibler, Joseph W. Experiments in Physical Chemistry. 8th. New York: McGraw Hill Higher Education, 2009. ISBN978--0--07-- 282842--9. Weast, Robert C. Physical Constants of Organic Compounds. CRC Handbook of Chemistry and Physics. 56th ed. 1976. C-76. Atkins, Peter and Julio de Paula. Physical Chemistry. 7th ed. New York: W. H. Freeman,2002. 235-238, 833-838. R. J. Silbey, R. A. Alberty, and M. G. Bawendi, Physical Chemistry (4th ed.) (Wiley, New York, 2004). R. Chang, Physical chemistry for the chemical and biological sciences (University Science Books, Sausalito, California, 2000).

EXPERIMENT 1
DETERMINATION OF Ka OF ACETIC ACID FROM CONDUCTANCE MEASUREMENTS

Submitted by: Pauline Bianca R. Alfonso Jean Annerie M. Hernandez Janine V. Samelo Nevah Rizza L. Sevilla Edessa Joy R. Sumagaysay