# Determining Equivalent Weight by Copper Electrolysis

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1 Purpose To determine the equivalent mass of copper based on change in the mass of a copper electrode and the volume of hydrogen gas generated during an electrolysis experiment. The volume of hydrogen gas will be used to calculate the number of moles of electrons passing through the cell. However, corrections for the vapor pressure and density of water must be applied prior to making the ideal gas law calculation. Introduction An electrochemical cell is a device that converts the energy of a chemical reaction into electrical energy. In such a cell, the chemical reaction proceeds by the transfer of electrons, this produces an electric current. A reaction that involves the transfer of electrons is an oxidation-reduction (redox) reaction. If the oxidizing and reducing species are separated from each other, the electron transfer can occur through a wire that is in contact with the oxidizing and reducing species. The flow of electrons through the wire (current) can be used to produce electrical work. The common dry cell battery is an electrochemical cell. When the terminals of a battery are connected to a motor, electrons will move from the cell through the motor produce work. If an electric current passes through a solution containing ions, positive ions move in one direction while negative ions move in the other direction. This movement of ions allows the current to pass through the solution. In order to maintain the current, chemical reactions must occur at the solution/electrode interface. These chemical reactions accompanying the passage of current are said to be the result a process called electrolysis, and the reactions that occur are oxidation-reduction reactions. Faraday s Laws describe the extent to which a chemical reaction occurs and the amount of electric current passed through the solution. These laws state that when Avogadro s number of electrons is supplied to a chemical system, one gram-equivalent of a chemical reaction will occur. The transfer of Avogadro s number of electrons corresponds to one Faraday of electricity. In this experiment we will determine the number of Faradays from the number of moles of hydrogen gas produced. In the electrolysis cell under study, the reduction reaction occurs in a slightly acidic medium. Hydrogen gas will be produced by the reduction of hydrogen ion: 2 H + (aq) + 2 e - H 2 (g) (1) Reduction will always occur at the cathode of an electrochemical cell. This is the negative pole in an electrolytic cell (as in this experiment), but is the positive pole in a voltaic (galvanic) cell. For every hydrogen ion reduced one electron will be required, and for every molecule of hydrogen gas produced two electrons will be required. By measuring the volume of hydrogen gas, and knowing the temperature and pressure of the gas, we can calculate the moles of hydrogen gas produced with the idea gas law. While hydrogen ion is being reduced at the cathode, a metal will be oxidized at the anode according to the reaction: M (s) M n+ (aq) + n e - (2) The relationship between a metal s atomic weight (AW) and the equivalent mass (EM) of the metal is shown by the equation: Revision F12 Page 1 of 7

2 AW = EM n (3) where n is the number of electrons the metal looses during the oxidation reaction. If the value of n is determined or known from a specific metal oxidation number, we can use equation (3) to determine the atomic weight of a metal with this experiment. For illustration, let us consider an electrolysis cell with an iron cathode and an inert anode. The chemical reactions that will occur are: Anode: Fe (s) Fe 2+ (aq) + 2 e - Cathode: 2 H + (aq) + 2 e - H 2 (g) If during the experiment moles of hydrogen gas is produced, the number of Faradays of electrons passing through the cell will be since each mole of hydrogen gas produced requires 2 moles of electrons. By weighing the iron electrode carefully before and after the experiment,, we observe the mass of the electrode decreases by grams. EM (iron) Grams iron = # Faradays oxidized passed grams (4) Since the ferrous ion has a charge of +2, we can apply Equation (3) and see that this result is consistent with the accepted atomic weight of iron, grams/mole. When the actual experiment is performed, two corrections must be applied to the observed values before the ideal gas law calculation can be made. First the hydrogen gas collected will be saturated with water vapor. The pressure of hydrogen gas and water vapor are independent of each other, as is explained in Dalton s law of partial pressures. P (Barometer) = P (Hydrogen) + P (Water Vapor) (5) The vapor pressure of water can be obtained by looking up the value in tables. Also during the experiment, the water level in the beaker will not be exactly the same as the water level in the gas buret. By estimating the difference and direction of the water level changes, another pressure correction will be made. The vapor pressure of water must be subtracted from the barometric pressure. If the water level in the buret is above the level in the breaker, this correction must be subtracted from the hydrogen partial pressure; if the water level in the buret is below the level in the breaker, this correction must be added. When making these corrections, it is critical that all pressures be measured in the same units. Most vapor pressure tables are given in units of mm of Hg. Since the density of mercury is 13.6 times greater than water, 1 mm Hg is equivalent to 13.6 mm of water. Finally when the ideal gas law calculations are made, the units for volume, pressure and temperature must be converted to the units of the ideal gas constant. Most commonly in chemistry we use: PV = nrt (6) where P is in atmospheres (1 atmosphere = 760 mm Hg), V is in liters, n is in moles, T is in Kelvin and the value of the ideal gas law constant R is (L atm)/(mol K). Make sure you check that all of your units cancel during these calculations. Revision F12 Page 2 of 7

4 6. Record the final electrolysis solution level for the first run on your data sheet. At this point, you should notice a coloration of the electrolysis solution from the copper ions created by oxidation of the copper electrode (REM: cupric ion is blue in aqueous solution). 7. Record the approximate distance (accurate to +/- 3 mm) between the solution level in the beaker and the gas buret. Record the value as a negative number if the solution level in the buret is above the level in the beaker. 8. Compress the pipette bulb and again draw the solution to a level between the 49 ml and 50 ml marks. Record the solution level on your data sheet. Wait a couple of minutes to check for gas leaks. Be certain the cathode wire is properly located within the end of the buret. 9. Place the copper electrode in the solution and repeat the electrolysis as before. You can stop whenever the total volume of hydrogen generated exceeds 92 ml, but do not allow the level to drop below the buret markings. Record your final gas level reading. 10. You should record the approximate distance (accurate to +/- 3 mm) between the solution level in the beaker and the gas buret, once again. Record the value as a negative number if the solution level in the buret is above the level in the beaker. 11. Make note of the barometric pressure in the laboratory and place a thermometer in the electrolysis solution. Record this temperature and use it for estimating the vapor pressure of water in the buret. 12. Carefully remove the connector wire from the copper electrode. Rinse the electrode with distilled water and acetone. Allow the electrode to dry completely and determine its mass on the same balance used for the initial determination. Revision F12 Page 4 of 7

5 Name: Data Sheet Final mass of copper electrode Initial mass of copper electrode Mass of copper oxidized during electrolysis g g g Barometric pressure (P barometer ) Temperature of solution after final electrolysis Vapor pressure of water (P water vapor ) o C First Run (Reference: ) Initial solution level Final solution level Volume of hydrogen gas (1st time) Difference between solution level in beaker and buret mm H 2 O Second Run Initial solution level Final solution level Volume of hydrogen gas (2nd time) Difference between solution level in beaker and buret mm H 2 O Total volume of hydrogen gas generated Average pressure of water column (avg water height divided by 13.6) (P water column ) Revision F12 Page 5 of 7

6 Name: Calculations (Show your work) Pressure of dry hydrogen gas ( P barometer - P water vapor + P water column ) Volume of hydrogen gas generated Temperature Liters Kelvin Moles of hydrogen generated (see equation #6) moles Faradays of current passed through cell (2 times # moles of hydrogen gas generated) faradays EM of copper (see equation #4) g / mole of charges Calculate the experimentally determined atomic weight of copper. Compare this to the accepted value and calculate your percent error: Revision F12 Page 6 of 7

7 Name: Pre-Lab Assignment In the electrolysis experiment similar to the one employed this experiment; a student observed that his unknown metal anode lost grams while a total volume of ml of hydrogen was being produced. The temperature of the solution was 25 o C and the barometric pressure was 740 mm Hg. The difference between the water levels in the beaker and burette was negligible. The vapor pressure of water at 25 o C is 23.8 mm Hg. 1. What is the pressure of the hydrogen gas in atmospheres? 2. What is the volume of hydrogen gas in liters? 3. Calculate the number of moles of hydrogen gas using the ideal gas law (For checking yourself, the answer is between and moles) 4. One mole of H 2 requires passage of Faradays 5. Number of Faradays passed = 6. EM = 7. The student was told the metal was oxidized to a 2 + oxidation state. What is the metal in the anode? Revision F12 Page 7 of 7

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