UNIVERSITI TUNKU ABDUL RAHMAN (UTAR) FACULTY OF SCIENCE UDEC 2194 CHEMISTRY LABORATORY III

EXPERIMENT No. : COMPONENT A, EXPERIMENT 4. TITLE : DETERMINATION OF CONDUCTANCES OF STRONG AND WEAK ELECTROLYTES.

LECTURER

: DR. SIM YOKE LENG

NAME OF STUDENT : NICOLE ANN FRANCIS FERNANDEZ ID NUMBER GROUP MEMBERS : 1003561 : TAN TAY YEE JACELYN MOHANA DASS CHONG WENG HSIANG

Objective: To measure the conductances of potassium chloride, hydrochloric acid, sodium chloride and sodium acetate, and to determine the dissociation constant of acetic acid.

Introduction: Molecular acids and bases consist of neutral molecules when pure. However, during dissolving, certain covalent bonds break to create ions. Thus electrolytes release free ions into the solvent. Those ions are free to move about in the solution and to carry current through the solution. Electrolytes are classed by how many ions they release into the solution. Some substances are 100% dissociated in solution; they are strong electrolytes. Soluble ionic compounds and a few acids like hydrochloric, nitric and sulfuric acids are strong electrolytes. Other substances release only a few ions into solution with the bulk of the substance remaining associated; these are weak electrolytes. All slightly soluble salts and many molecular acids and bases (except the strong ones) are weak electrolytes. Electrolyte solutions obey Ohm's law just as metallic conductors do. Thus the current, I, passing through a given body of solution is proportional to the applied potential difference, V. The resistance, R, of the body of solution in ohms () is given by R = V/I. where the potential difference is expressed in volts and the current in amperes. The conductance, defined as the reciprocal of the resistance, of a homogeneous body of uniform cross section is proportional to the cross-sectional area A and inversely proportional to the length :

1 = R

where is the specific conductance with units -1m-1 . Since it is difficult to build a cell with well defined geometrical parameters A and , any cell should be calibrated with a solution of exactly known specific conductance. We can determine the cell constant K:

K A The cell constant, K, with units cm-1, is determined by measuring the resistance of a cell filled with a solution of known specific conductance, which is here KCl. Once the cell constant K has been determined, specific conductances of any solution can be calculated from experimental resistances. The specific conductance increases as the concentration increases. A more fundamental unit of electrolytic conductance is the equivalent conductance , which can be thought as the value of contributed by one equivalent of ions contained in 1000 cm3 of solvent. It is defined as: = R

1000 = c The units of concentration, c, are equiv/L and the units of are cm2equiv-1ohm-1. Note, that in the case of simple one-one electrolytes A+B-, there is no distinction between equivalents and moles and the equivalent conductance is the same as the molar conductance.

A strong electrolyte is a solute that completely, or almost completely, ionizes or dissociates in a solution. While the specific conductance of a solution increases with concentration, the

equivalent conductance decreases as the concentration increases. Theoretically, for strong electrolytes in dilute solution that the effect of ionic attraction reduces the equivalent conductance.

= 0 (A+B 0) C Below concentrations of about 0.1M, a plot of against c gives a straight line, the intercept of which equals , the equivalent conductance at infinite dilution. At infinite dilution the ions act completely independently, and it is then possible to express 0 as the sum of the limiting conductances of the separate ions.

For weak electrolytes, the Ostwald dilution laws gives us: 1/ = 1/o + C / ka o2

Apparatus and materials: Conductivity meter, dilution flasks (100ml), pipette, burette, 0.2M KCl solution, 0.1M acetic acid, 0.1M HCl, 0.1M NaCl solution and 0.1M sodium acetate solution.

Procedure: 1. Determination of cell constant

The conductance (L) of 0.2M KCl solution was measured. The specific conductance (X) of this solution was 2.768 x 10-3 ohm-1 cm-1. The cell constant was determined.

2. Measurement of conductance From the solution of acetic acid provided, a succesive dilution with conductivity water solution of 0.0500, 0.0250, 0.0125, 0.00625, 0.00312, 0.00156 and 0.00078M.

Measure the conductances of these solutions. Repeat with HCl, NaCl and sodium acetate.

The conductance of the water used was measured.

Results: Conductances of the solutions Conductance (-1) C (mol dm ) CH3COOH 0.1000 0.0500 0.0250 0.0125 0.00625 0.00312 0.00156 0.00078 564 s 404 s 286 s 198 s 139 s 96 s 67 s 46 s HCl 42.5 ms 20.9 ms 10.8 ms 5.46 ms 2.78 ms 1373 s 685 s 344 s NaCl 11.42 ms 3.95 ms 2.02 ms 1032 s 526 s 260 s 135.3 s 67.4 s CH3COONa 7.55 ms 3.92 ms 2.02 ms 1034 s 522 s 266 s 132.7 s 67.4 s
-3

Conductance of distilled water = 9 x 10-6 Conductance of KCl = 0.0262 -1

Cell constant, k = X / L = (2.768 x 10-3 -1 cm-1) / 0.0262 -1 = 0.1057 cm-1

Specific conductances of the solutions Specific conductance, X (-1cm-1) C (mol dm ) CH3COOH 0.1000 0.0500 0.0250 0.0125 0.00625 0.00312 0.00156 0.00078 5.96 x 10-5 4.27 x 10-5 3.02 x 10-5 2.09 x 10-5 1.46 x 10-5 1.01 x 10-5 7 x 10-6 4.8 x 10-6 HCl 4.492 x 10-3 2.209 x 10-3 1.142 x 10-3 5.771 x 10-4 2.938 x 10-4 1.451 x 10-4 7.24 x 10-5 3.63 x 10-5 NaCl 1.207 x 10-3 4.175 x 10-4 2.135 x 10-4 1.09 x 10-4 5.55 x 10-5 2.74 x 10-5 1.43 x 10-5 7.1 x 10-6 CH3COONa 7.98 x 10-4 4.143 x 10-4 2.135 x 10-4 1.092 x 10-4 5.51 x 10-5 2.81 x 10-5 1.4 x 10-5 7.1 x 10-6
-3

Molar conductivity, (-1 cm2 mol-1) of four electrolytes C1/2 C (mol cm ) (mol cm-3)1/2 1.0 x 10-4 0.01 CH3COOH 0.596 HCl 44.92 NaCl 12.07 CH3COONa 7.98
-3

Molar conductivity, (-1 cm2 mol-1)

5.0 x 10-5 2.5 x 10-5 1.25 x 10-5 6.25 x 10-6 3.12 x 10-6 1.56 x 10-6 0.78 x 10-6

7.071 x 10-3 5.000 x 10-3 3.536 x 10-3 2.500 x 10-3 1.766 x 10-3 1.249 x 10-3 8.832 x 10-4

0.854 1.208 1.672 2.336 3.237 4.487 6.154

44.18 45.68 46.168 47.008 46.506 46.41 46.538

8.35 8.54 8.72 8.88 8.782 9.167 9.103

8.286 8.54 8.736 8.816 9.006 8.974 9.103

Graph of versus C1/2 for HCl

47.5 47

(-1 cm2 mol-1

46.5 46 45.5 45 44.5 44 0 0.002 0.004 0.006 0.008 0.01 0.012

C1/2

[ (mol

cm-3)1/2

Graph of versus C1/2 for NaCl

9.4 9.2

(-1 cm2 mol-1

9 8.8 8.6 8.4 8.2 8 0 0.001 0.002 0.003 0.004 0.005 0.006 0.007 0.008

C1/2 [ (mol cm-3)1/2

9.4 9.2 9

(-1 cm2 mol-1

8.8 8.6 8.4 8.2 8 7.8 0 0.002 0.004 0.006 0.008 0.01

C1/2

[ (mol

cm-3)1/2

1 / and C values for acetic acid 1 / ( cm-2 mol) 1.678 1.171 C (mol cm-3) (-1 cm2 mol-1) 5.96 x 10-5 4.27 x 10-5

0.828 0.598 0.428 0.309 0.223 0.162

3.02 x 10-5 2.09 x 10-5 1.44 x 10-5 1 x 10-5 6.9 x 10-6 4.3 x 10-6

Graph of 1/ versus C
1.8 1.6 1.4 1.2 1 0.8 0.6 0.4 0.2 0 0 0.00001 0.00002 0.00003 0.00004 0.00005 0.00006 0.00007

1/ (-1 cm2 mol-1)

C (mol cm-3) (-1 cm2 mol-1)

Calculation of 0 for CH3COOH using Kohlrauschs law 0 (HCl) = 46.9 -1 cm2 mol-1

0 (NaCl)

= 9.18 -1 cm2 mol-1

0 (CH3COONa) = 9.16 -1 cm2 mol-1

By using Kohlrauschs law,

0 (CH3COOH)

= 0 (CH3COONa) +0 (HCl) 0 (NaCl) = (9.16 + 44.9 9.18) -1 cm2 mol-1 = 46.88 -1 cm2 mol-1

The degree of dissociation of CH3COOH at the concentrations of 0.0500, 0.0125 and 0.00156 M: At 0.05000 M, = 0.854, = / 0 = 0.854 / 46.88 = 0.0182

At 0.01250 M, = 1.672,

= / 0 = 1.672 / 46.88 = 0.0357

At 0.00156 M, = 4.487,

= / 0 = 4.487 / 46.88 = 0.0957

The dissociation constant of CH3COOH:

2C ka = 1- (0.0182)2 (0.05 mol dm-3) = 1 0.0182 = 1.687 x 10-5 M

Calculation of ka and 0 from graph of 1/ versus C:

Gradient of graph, __1 = ka

2 0

_(1.6 0.8) cm-2 mol _ (5.8 2.8) x 10-5 -1 cm-1 = 26666.67 mol cm-3 = 2.6667 x 107 mol dm-3

ka20 = 1 / (2.6667 x 107 mol dm-3) = 3.75 x 10-8 mol-1 dm3

The intercept at C = 0, 1 = 0.04 cm-2 mol 0 0 = 1 / (0.04 cm-2 mol) = 25.0 -1 cm2 mol-1 = 25.0 -1 (0.1dm)2 mol-1 = 0.25 -1 dm2 mol-1

Equilibrium constant, ka = ka20 /20 = 3.75 x 10-8 mol-1 dm3 / (0.25 -1 dm2 mol-1)2 = 6 x 10-7 2 mol dm-1

Theoretical dissociation constant of acetic acid (ka) = 1.4 x 10-5 M. The experimental value of ka = 1.687 x 10-5 M.

1.687 x 10-5 M 1.4 x 10-5 M Percentage error of ka = x 100% 1.4 x 10-5 M

= 20.5 %

The theoretical value of molar conductivity in the limit of zero concentration of acetic acid, 0 = + + = 34.96 + 4.09 = 39.05 mS m2 mol-1 From calculation, the experimental value of 0 is 46.88 -1 cm2 mol-1(from Kohlrauschs law). (46.88 39.05) -1 cm2 mol-1 Percentage error of0 = x 100% 39.05 cm mol
-1 2 -1

= 20.05 %

Discussion: The conductivity of HCl, which was a strong electrolyte, was found to be 46.9 -1 cm2 mol-1, while the conductivity of NaCl was 9.18 -1 cm2 mol-1. The conductivities of the weak electrolytes, CH3COOH and CH3COONa were 46.88 -1 cm2 mol-1 and 9.16 -1 cm2 mol-1 respectively. The conductance of an electrolyte depends upon the number of ions present in the solution. So, the greater the number of ions in the solution the greater is the conductance. The number of ions produced by an electrolyte depends upon its nature. The strong electrolytes dissociate almost completely into ions in solutions and their solutions have high conductance. On the other hand, weak electrolytes, dissociate to only small extents and give lesser number of ions. Therefore, the solutions of weak electrolytes have low conductance. The molar conductance of electrolytic solution varies with the concentration of the electrolyte. In general, the molar conductance of an electrolyte increases with decrease in concentration or increase in dilution. The variation of molar conductance with concentration can be explained on the basis of conducting ability of ions for weak and strong electrolytes. For weak electrolytes the variation of with dilution can be explained on the bases of number of ions in solution. The number of ions furnished by an electrolyte in solution depends upon the degree of dissociation with dilution. With the increase in dilution, the degree of dissociation increases and as a result molar conductance increases. The limiting value of molar conductance (x) corresponds to degree of dissociation equal to 1, which means that the whole of the electrolyte dissociates. Thus, the degree of dissociation can be calculated at any concentration as, = /x

where is the degree of dissociation, is the molar conductance at concentration C and x is the molar conductance at infinite dilution. By definition, in strong electrolytes, there is no increase in the number of ions with dilution because strong electrolytes are completely ionised in solution at all concentrations. However, in concentrated solutions of strong electrolytes there are strong forces of attraction between the ions of opposite charges called inter-ionic forces. Due to these inter-ionic forces the conducting ability of the ions is less in concentrated solutions. The ions become far apart from one another and inter-ionic forces decrease when a solution is diluted, and this causes the molar conductivity to increase. When the concentration of the solution becomes very low, the inter-ionic attractions become negligible and the molar conductance approaches the limiting value called molar conductance at infinite dilution. This value is characteristic of each electrolyte. The conductivity of an electrolyte also depends upon the temperature. With increase in temperature, the conductivity of an electrolyte increases.

Conclusion: The conductivity of HCl, which was a strong electrolyte, was found to be 46.9 -1 cm2 mol-1, while the conductivity of NaCl was 9.18 -1 cm2 mol-1. The conductivities of the weak electrolytes, CH3COOH and CH3COONa were 46.88 -1 cm2 mol-1 and 9.16 -1 cm2 mol-1 respectively. The dissociation constant of acetic acid was 1.687 x 10-5 M.

References: 1. Atkins Physical Chemistry , Peter Atkins and Julio de Paula, (8th edition), Oxford New York 2. Electrolytes and Non-Electrolytes. Retrieved 11th March 2012 from http://web.clark.edu/aaliabadi/F08Electrolytes 3. Conductance, Specific Conductance and Molar Conductance. Retrieved 11th March 2012 from http://www.askiitians.com/iit-jee-chemistry/physical-chemistry/ElectrolyticConductance-Molar-Conductance-and-Specific-Conductance-page5.aspx