Experiment 3 : Electrode and its use Objectives : 1) To introduce the types of electrode that is important in electrochemistry and environment

research. 2) To introduce the use of glass electrodes in the determination of ionization constants weak poly acid. 3) To investigate the hydrolysis reaction by using glass electrode. Introduction: There are many types of electrode that can be use to build electrochemical cell. Electrodes are divided into several groups which are gas electrode, salt insoluble metal electrode, metal electrodes and membrane electrode. a) Gas electrode This type of electrode constructed with an inert metal, surrounded by bubble-bubble gas. It should be soaked in a solution containing ions of the gas such as hydrogen electrode. Hydrogen electrode is the electrode and the reference standard for all other types of electrodes. By definition, it has a capacity equal to zero electrode. b) salt insoluble metal electrode This group of electrodes made of a metal immersed in saturated salt larutaan. Common salt normally has very low solubility. These are two examples elektrode silver chloride electrode (Ag, AgCl) and kalomel electrodes (Hg, Hg2Cl). This is because, both electrodes are easier to use than the hydrogen electrode, they are often used as a secondary standard electrode. c) metal electrode Metal electrodes consist of metal immersed in a solution of soluble salt. For example, are the electrode zinc (Zn, ZnSO4) and copper electrode (Cu, CuSO4) in Daniells Cell. d) Membrane electrode

Electrode consists of a piece of semi-permeable membrane, and can measure the difference between the activity of ions in the solution of both membrane. This electrode group is very useful in environmental studies. The examples of this type of electrode are the electrode selector ions (important in the analysis of ions such as chloride ions and ammonium ions) and a glass electrode (measuring pH or ion H+) In this experiment, glass electrodes are use for determination of the ionization constant of phosphoric acid and measurement of the degree of hydrolysis and the equilibrium constant. A. Determination Of Ionization Constant Of Phosphoric Acid Ionization of Phosphoric Acid: H3PO4 H2PO4 HPO42H2PO4- + H+ HPO42- + H+ PO43- + H+
K =( 1 K =( 2 K =( 3

)(

)(

)(

The third ionization step occurs at a very high pH. Therefore, the K3 cannot be determined in aqueous solution method. The first and second ionization steps to complete the pH change of solution occurred. pK1 and pK2 given by the following references: Log K1 = log(H+) + log pH pH = -logK1 + log = pK1+ log
( ( ( )

(3.1)

and log K2 =log (H+) + log

(3.2)

From equation, (3.1) and (3.2), it is cleared that, (H2PO4) = (H3PO4) and (HPO4-) = (H2PO4-), the pH = pk. This occurs when half of the volume of alkali that necessary for neutralization was added. Therefore, PK can be obtained from the titration curve at V / 2 in which the total volume of alkali necessary for neutralization. To poly acid, K usually be completed before the second

step begins. Therefore, the titration curve will have two points clear, and this equivalence allows the pK1 and pK2 read from these curves.

b. Test for the reaction of hydrolysis of Aniline hydrochloride In aqueous solution, aniline hydrochloride will undergo hydrolysis by following steps: C6H5.NH3Cl C6H5.NH3+ + H2O C6H5.NH3+ + Cl C6H5.NH2 + H3O+

If constant of this hydrolysis process is Kh and degree of hydrolysis is , thus Kh =

( )( )

Where C is the concentration of aniline hydrochloride in solution (mol L-1) When C H3O+ = C Therefore, if pH is measure, can be determined and Kh can be calculated.

Apparatus: pH meter, glass electrode, burette, pipette, volumetric flask Chemicals: Standardize NaOH solution (0.10 M), Sulfuric acid, H3PO4(0.10M), Aniline chloride solution (0.10M)

Procedure A. Determination of ionization constant of phosphoric acid 5mL 0.1M H3PO4 was pipette into the beaker and put electrode inside the beaker. pH of H3PO4 solution was measured.

0.1M NaOH

H3PO4 was titrated with 0.1M NaOH and the pH was measured after every 2mL of NaoH added.

H3PO4 solution

When the titration is near the end-point (can be detected when pH suddenly occur a lot of changes), addition of NaOH was decreased to 0.5mL until the end-point of titration.

Two end-point should be detected. After the experiment ended, the electrode washed and immersed into distilled water to let it in good condition

B. Determination of degree (0) and constant of hydrolysis aniline hydrochloric Solution of 0.1M aniline hydrochloric was diluted to prepared concentration solution for 0.05M, 0.01M, 0.005M, 0.001M, 0.0005M, 0.0003M and 0.0001M

Results: Volume of NaOH added (mL) 2.0 4.0 6.0 6.5 7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0 11.5 pH of H3PO4 5.31 5.45 7.65 7.91 8.11 8.20 8.29 8.37 8.53 8.68 8.84 9.16 10.10 11.23

M1V1 = M2V2 Concentration of aniline hydrochloride (M) a. b. c. d. e. f. g. 0.5 0.01 0.005 0.001 0.0005 0.0003 0.0001 Volume of aniline hydrochloride (mL) 50 10 5 1 0.5 0.3 0.1 5.10 5.38 5.47 5.47 5.30 5.30 5.92 pH

Data analysis Calculation for Part A: From the graph,

pKa1= 5.3 and pKa2= 8.3 pH= 6.6 at first equivalence point and pH= 10.1 at second equivalence point

Substitute the values of pH= 6.6 and pKa1= 5.3 into equation (2)

Substitute 1.3 into equation (1)

-logKa1= 6.6 - 1.3 logKa1= -5.3 Ka1=10-5.3 Ka1= 3.16

Substitute the values of pH= 10.1 and pKa1= 8.3 into equation (2)

Substitute 1.6 into equation (1)

-logKa2= 10.1 1.8 logKa1= -8.3 Ka2= 10-8.3 Ka2= 5.01 x 10-9

Calculation for Part B: pH = -log [ H3O+ ] From the data: (i) (a) pH log [H3O+] [H3O+] (b) pH log [H3O+] [H3O+] = 5.10 = -5.10 = 7.94 x 10-6M = 5.38 = -5.38 = 4.17 x 10-6M

(c) pH log [H3O+] [H3O+]

= 5.47 = -5.47 = 3.39 x 10-6M

(d) pH log [H3O ] [H3O ] (e) pH log [H3O ] [H3O ] (f) pH log [ H3O+ ] [H3O+] (g) pH log [H3O+] [H3O+] (ii) [H3O+] = c Kh =
+ + + +

= 5.52 = -5.52 = 3.02 x 10-6M = 5.30 = -5.30 = 5.01 x 10-6M = 5.70 = -5.70 = 2.00 x 10-6M = 5.92 = -5.92 = 1.20 x 10-6M

(a) [H3O+] C

= 7.94 x 10-6M = 7.94 x 10-6M = = 1.59 x 10-4

Kh

)(

= 1.26 x 10-9 (b) [H3O+] C = 4.17 x 10-6M = 4.17 x 10-6M = = 4.17 x 10-4

Kh

)(

= 1.74 x 10-9 (c) [H3O+] C = 3.39 x 10-6M = 3.39 x 10-6M

= = 6.78 x 10-4

Kh

)(

= 2.30 x 10-9 (d) [H3O+] = 3.02 x 10-6M C = 3.02 x 10-6M

= 3.02 x 10-3

Kh

)(

= 9.15 x 10-9

(e)

[H3O+] = 5.01 x 10-6M C = 5.01 x 10-6M

= = 0.01 Kh =

)(

= 5.05 x 10-8 (f) [H3O+] = 2.00 x 10-6M C = 2.00 x 10-6M

= = 6.67 x 10-3

Kh

)(

= 1.34 x 10-8

(g) [H3O+] = 1.20 x 10-6M C = 1.20 x 10-6M

= = 0.012

Kh

)(

= 1.46 x 10-8

Discussion An electrode is an electrical conductor used to make contact with a nonmetallic part of a circuit (e.g. a semiconductor, an electrolyte or a vacuum). Electric currents are run through nonmetal objects to alter them in numerous ways and to measure conductivity for numerous purposes. A) Determination of Ionization Constant of Phosphoric Acid The reaction between weak acid, phosphoric acid with strong base, sodium hydroxide is as bellow: H3PO4 + NaOH NaH2PO4 + H2O Titration of phosphoric acid solutions with a strong base such as sodium hydroxide yield two clear equivalence points corresponding to the reaction of the first, and second proton of phosphoric acid with hydroxide ion. The phosphoric acid is a polyprotic acid that has three different pKa values, one for the removal of each of its three
-

protons.

In

this

experiment,

the

solution

begins with H3PO4. As base is added, H2PO4 and H3PO4 are found in the solution. H3PO4 H2PO4- + H+

Eventually, only H2PO4- can be found in the solution, and the first equivalence point is reached, pH at equivalence point is 6.6. At pKa1= 5.3, Additional base does not result in an overwhelming of the system with OH- ions, as it does in monoprotic acids. The hydroxide ion is instead used to remove the second proton. This is more difficult than the first removal. The addition of base creates in the solution both H2PO4- and HPO42-. Eventually, the solution only contains this ion, and the second equivalence point is reached. The amount of base needed to go from the first equivalence point to this second determines the new half equivalence point where H2PO4- and HPO42- can be found in equal concentrations. Experimentally this value is 10.1, as compared with the known pKa2= 8.2. The addition of more base is used to remove the third proton, but in this experiment that was not attempted for time considerations.

The precaution that should be taken while doing this experiment is during titration with sodium hydroxide, we should pay special attention to its concentration. Strong base solutions are not stable as they tend to absorb atmospheric carbon dioxide. In the case of phosphoric acid we should additionally be careful about end point detection. B. Determination of Degree (0) and Constant of Hydrolysis Aniline Hydrochloric In this part, two solutions is dilute to form the needed concentration of aniline hydrochloric which are 0.05M, 0.01M, 0.005M, 0.001M, 0.0005M, 0.0003M and 0.0001M . From the result, the pH of aniline hydrochloric is constant at range 5.0 to 6.0. This is due to the solution is diluted by different volume of distilled water. It may affect the value of , and hydrolysis constant (Kh). From the result, the higher the concentration of aniline hydrochloride formed from its 0.1 M concentration, the lower the hydrolysis constant. The precaution that should be taken while doing this part is, the accuracy of measurements of aniline hydrochloric and distilled water volume. This may lead to unaccuracy of measurement.

Conclusion: After conducting this experiment, we know that the types of electrode that is important in electrochemistry and environment research which are glass electrode, gas electrode, salt insoluble metal electrode, metal electrode, and membrane electrode. In order to determine the ionization constant of weak poly acid, glass electrode can be useful. For example, the hydrolysis of aniline hydrochloric to dilute solution can use glass electrode for determine its degree and constant of hydrolysis.

References 1. Athawale V.D, Mathur Parul, Experimental Physical Chemistry, New Age International (P) Limited, Publisher , New Delhi, 2001 2. Dennis G. Peters, John M. Hayes, Gary M. Hieftje. Aqueous Acid-Base Reactions. Chemical Separations and Measurements; W.B. Saunders Company: Philadelphia, 1974; 132. 3. Suchacki John, Conceptual Chemistry, 3rd edition, 2007, Pearson Benjamin Cummings. 4. Spencer James N., Bodner George M., Rickard Luqman H., Chemistry Structure and Dynamics, 2nd edition,2003, John Wiley and Son, United States of America. 5. Tro Nivaldo J., Introductory Chemistry, 3rd edition, 2009, Pearson Prentice Hall.