Experiment 4: Homogeneous Gaseous Equilibrium The Dissociation of N2O4

CHM 3011

Preparation
To make dry ice, take the small cooler into Rm 212. Keeping the door ajar, close the dry ice maker, making sure the latch is secure. Open the CO2 tank by turning the handle counterclockwise for several revolutions. You should hear a hiss and see a white fog seeping out of the maker. When the sound changes from a hiss to a loud sound through the safety valve on top of the maker, quickly close the tank. Open the dry ice maker and remove the dry ice cake with paper towels *Caution: Do not allow bare skin to touch the dry ice as this will result in a severe burn. Place the cake into the cooler. *Click on picture for video Please note that it will take approximately 3040s for the dry ice to be made. The video does not show this waiting period.

Preparation
Break the dry ice cake into small pieces and add it slowly to the Dewar flask containing isopropyl alcohol. The aim is to cool the trap so that the N2O4/NO2 mixture is condensed before reaching the pump. Dry ice is warm enough that any air in the system is pumped through the trap. The alcohol provides good thermal contact between the dry ice and trap. *Click on picture for video

Procedure
Take the Dumas (gas) bulb and, if necessary, lubricate the stopcock with a minimum quantity of Corning grease. Connect the bulb to the vacuum manifold and exhaust to a pressure of 12mm. *Click on picture for video

Procedure
Remove the evacuated bulb and weigh it to 0.1mg. a. Clean the bulb with a Kimwipe and place in the balance. b. Turn the left side knob to Preweigh. c. The illuminated number on the front of the balance should be approximately 70. Turn the left side knob to the off position. d. Enter the value of the illuminated number using the front-left knob for the tens of grams and the frontright knob for unit grams. e. Turn the left-side knob to Full Release. f. Use the right side knob to align the black bar with the illuminated number. g. Record the mass. *Click on picture for video

Procedure

The partially evacuated bulb has buoyancy that causes the mass to drift somewhat; for this reason, take at least four readings for each mass measurement throughout the experiment.

Procedure
Fill the bulb with dry air at atmospheric pressure by allowing the air to enter through a CaSO4 drying tube. Close the stopcock and reweigh the bulb. *Dont forget to replace the black cap and pinch collar on the CaSO4 drying tube. *Click on picture for video

Procedure
*Refer to the next slide for pictures.

Measure the atmospheric pressure on the barometer and record the room temperature using the thermometer on the barometer. Adjust the level of the reservoir by using the cistern to adjust the screw until the level just touches the tip of the white pointer in the cistern. Move the sliding vernier scale until the front and back of its bottom are even with the top of the convex mercury meniscus. Read the height to the nearest millimeter from the position of the vernier bottom on the fixed scale. Use the vernier to read to the nearest 0.1mm by noting which line on the vernier matches a line on the fixed scale. Correct the mercury height to what it would be at 0 C by using the chart to the side of the barometer to determine the amount to subtract from the reading at room temperature and the pressure reading.

Use the sliding vernier to measure the height of the mercury column.

Adjust the screw until the mercury reservoir just touches the tip of the white pointer in the cistern.

Cistern adjusting screw

Procedure
Under the supervision of the instructor, evacuate the Dumas bulb again and fill the bulb with the N2O4/NO2 mixture to atmospheric pressure. *CAUTION: Dinitrogen tetroxide is corrosive and very poisonous; all operations should be carried out with care. *Click on picture for video

Procedure
Attach the capillary tip with tygon tubing to the top of the bulb before placing it in the bath. *Click on picture for video

Procedure
Immerse the bulb in a water bath regulated to about 40C with the stopcock and stem of the bulb held vertically above the water. As soon as the bulb is in the bath, place the funnel, which is attached to house vacuum, a centimeter above the end of the capillary. Keep the temperature constant to within 0.1C for at least ten minutes. *Click on picture for video

Procedure
Using the funnel to catch the escaping gas, repeatedly open the stopcock momentarily until the loss of brown fumes is negligible and the gas mixture is at atmospheric pressure; then be certain the stopcock is closed. Record the temperature immediately before and after this procedure. *Click on picture for video

Procedure
Remove the capillary tip and allow the bulb to cool by placing it in a beaker of water for 5 minutes. Read the barometer. *Click on picture for video

Procedure
Dry the bulb carefully, and then weigh it to the nearest 0.1mg. Since the contents of the bulb are below atmospheric pressure when the bulb is below the bath temperature, opening the stopcock except when the bulb is in the bath will contaminate the gas mixture with air and ruin the results. If this should occur, a new sample of gas is required; see the instructor. *Click picture for video

Procedure

Repeat the previous steps, starting with the immersion of the bulb in the water bath, at five additional temperatures 5-7 apart, each time holding the temperature constant to 0.1. To save time, raise the bath temperature while the bulb is being cooled and weighed. Allow about 10 minutes at each new temperature to make certain the bulb has reached equilibrium with the bath before opening the stopcock.

Calculations and Discussion

Use the following slides as an example for the plots and calculations required in this lab report. The following slide shows sample data that has been inputted into the provided Excel spreadsheet. Note that the columns highlighted in yellow contain the collected experimental data. The remaining columns contain values calculated by the program.

Florida Tech CHM 3011 Homogeneous Gas Equilibrium Barometric Press (torr) = 762.9 Mass of empty bulb = Density dry air (g/mL) = 1.205E-03 Mass of bulb with air = Volume of bulb (L) = 1.940E-01 Do not skip or delete cells below! Temp Mass filled bulb Mass gas T 1/T 41.5 71.2011 0.5492 314.7 3.178E-03 47.0 71.163 0.5111 320.2 3.123E-03 52.5 71.1325 0.4806 325.7 3.070E-03 59.5 71.1024 0.4505 332.7 3.006E-03 63.1 71.0816 0.4297 336.3 2.974E-03 71.8 71.0618 0.4099 345.0 2.899E-03 70.6519 70.8857

Alpha 0.2636 0.3345 0.3952 0.4571 0.5113 0.5443

K 0.2999 0.5058 0.7432 1.0606 1.4212 1.6908

ln(K) -1.2044 -0.6816 -0.2967 0.0589 0.3515 0.5252

slope= -6288.97566 intercept = 18.91983 std dev = 604.3139489 std dev = 1.838866 Equillibrium constant at 298 K = DG (kJ/mol) at 298 K = DH (kJ/mol) = DS (J/deg-mol) at 298 K = 5.39 52.29 157.30 0.1138 +/-9.6 +/-5.0 +/-15.3

To explain the computer results, provide the following sample calculations for one of your temperatures: = 0.001293P (1 + 0.00367t)*760 where t = temperature in degrees Celsius

Use the density of the air and the weights of the Dumas bulb when evacuated and when filled with dry air, to calculate the volume of the bulb.
Use the following equations to calculate a and KP: a = MPV - 1 WRT KP = 4a2P 1a2 where M = molecular weight of undissociated N2O4 P = the corrected barometric reading in atmospheres V = volume of bulb W = weight of gas in bulb R = gas constant T = temperature in Kelvin *Be sure to record your calculated values and the computer values for your temperature in the following format: V C W T 1/T a KP lnKP

Calculations
Note: The results given here do not include the correct number of significant figures. This will be determined by your error analysis.

The Excel spreadsheet will automatically create a plot of lnK vs. 1/T and provide the slope and y-intercept.
ln(K)

Homogeneous Gas Equilibrium

0.8 0.6 0.4 0.2 0.0 -0.2 -0.4 -0.6 -0.8 -1.0 -1.2 -1.4 2.8E-03

2.9E-03

3.0E-03 1/T

3.1E-03

3.2E-03

Obtain the value of KP at 298K by using the slope and intercept from the lnK vs 1/T plot. Then, use the following formula to obtain the value of DG298: DG = -RTlnKP = ______kJ/mol Obtain DH by using the following formula: slope = -DH/R DH = -slope*R = ______kJ/mol Using the Gibbs equation, calculate the entropy for dissociation: DG = DH TDS DS = DH DG T = ______J/mol

Calculations

Compare your values (in kJ/mol) with those from literature for DG, DH, and S.