CHM 202 Laboratory

COMPUTATIONAL CHEMISTRY USING SPARTAN

Before you start, create a folder to save your work in: 1. Open My Computer on Windows Desktop 2. Navigate to: C:\Documents and Settings\Workstation.MS109XXX\My Documents 3. Create new folder and name it using your initials or name Open SPARTAN and maximize window. Experiment 19A Heats of Formation Part One: Isomerism (determining relative stabilities of cis- and trans-2-butenes) 1. Build cis-2-butene model 2. Minimize its geometry (energy): click E button on toolbar 3. Calculate molecules heat of formation: a. Setup Calculations select Equilibrium Geometry and Hartree-Fock/631G Submit b. When prompted for filename, navigate to your folder and Save As cis-2-butene c. When prompted, click OK and wait 1-3 minutes d. At completed prompt, click OK 4. Display properties: Display Properties 5. Record the Energy in units of au 6. Convert energy to units of kJ/mol (2625 kJ/mol per au) you may use SPARTANs calculator by clicking Options menu at top right and opening it 7. Close cis-2-butene session 8. Repeat Steps 1-6 for trans-2-butene - remember to save file as trans-2-butene when prompted 9. What is the energy difference between the isomers and which is more stable? Answer questions in manual. Part Two: Acetone and Its Enol 1. Build acetone model 2. Minimize its geometry (energy) 3. Calculate heat of formation using the equilibrium geometry & Hartree-Fock/6-31G settings when prompted, save as acetone 4. Open Properties and record the heat of formation (Energy in au), then convert to kJ/mol 5. Close acetone session 6. Repeat Steps 1-5 for the enol of acetone, saving the file as enol when prompted 7. Note which enol conformer was calculated above and repeat Steps 1-5 for conformer having the OH groups rotated by 180: a. After Step 1, click the Measure Dihedral Angel button b. Select the atoms in C=C-O-H in sequence c. Change the angle in the box at bottom right of window to 0 or 180 as appropriate

Fechter CHM202 Spring 2009

d. Click on the workspace and continue to Step 2 8. Calculate the energy differences between acetone and the two enol forms, and answer the questions in the manual. Which enol form is more stable? Rationalize. Part Three: Regioselectivity (comparing 1 and 3 carbocations of isobutane) 1. Build isobutane model 2. Delete a 1 H and the remaining valence 3. Minimize geometry 4. Calculate heat of formation: a. Setup Calculations select Equilibrium Geometry, Hartree-Fock/631G, and Total Charge:Cation Submit b. When prompted, Save As isobutyl-1-yl cation 5. Open Properties and record Energy, then convert au to kJ/mol units 6. Close session 7. Repeat Steps 1-6, but a. In Step 2, delete a 3 H and remaining valence b. Save As isobutyl 3-yl cation when prompted 8. Answer questions in manual Experiment 19C Density-Electrostatic Potential Maps Acidities of Carboxylic Acids In this experiment, it is important to orient the OH of the carboxyl group properly, or the results will be not be clear. 1. Build acetic acid model 2. Adjust the H-O-C=O dihedral angle to 0 3. Minimize geometry 4. Generate the electron density map: a. Setup Surfaces b. Add c. Select Surface: Density and Property: Potential d. Setup Submit e. When prompted, Save As acetic acid f. When done calculating, click OK g. Check line entry in Surfaces dialog box h. Note colors: red ~ high electron density (-); blue ~ low electron density (+) 5. Close session 6. Repeat Steps 1-5 for chloroacetic acid and then for trichloroacetic acid (remember to name files appropriately when prompted) 7. Open all three files 8. Arrange the molecules on the workspace in the order: CH3CO2H, ClCH2CO2H, Cl3CCO2H; make sure that the density maps show 9. Click on the acetic acid model to select it (confirm name in Title Bar of SPARTAN window at top left) 10. Obtain relative density value of acidic H: a. Display Properties b. Click on model till crosshair box appears c. Record max value on blue (right) side of bar

Fechter CHM202 Spring 2009

11. Repeat Steps 9-10 for chloroacetic acid and trichloroacetic acid, in turn 12. Turn off the density plots by unchecking the entries in the Surface dialog boxes 13. Measure and record the O-H bond lengths for each acid 14. Compare density and bond length values for the three acids and rationalize. [Regarding O-H bond lengths, result was not what I expected: they were all ~same. Dont know why.]] Hydrogen Bonding Experiment Water: Display and measure covalent O-H bond and H-bond lengths in a cluster of water molecules. 1. Build a water molecule 2. Add a new water molecule to the workspace by holding Insert key and adding first atom of molecule 3. Repeat Step 2 until there are 20-30 molecules showing. Rotate space occasionally while adding molecules to obtain a 3-D cluster 4. Minimize geometry/energy 5. Model Hydrogen Bonds 6. Measure covalent O-H bond and H-bond lengths and record. 7. Compare the bond lengths and comment. Acetic Acid Dimer: In this experiment, it will be important to (1) properly orient the OH of the carboxyl group and (2) to properly position the second acetic acid molecule close to the first in order to obtain the desired results. 1. Build acetic acid 2. Set the H-O-C=O dihedral angle to 0 3. Build the 2nd acetic acid molecule by first pressing Insert key and adding first atom (suggest using sp2 O and placing it near OH of first molecule), then complete and repeat Step 2 4. Minimize geometry 5. Model Hydrogen Bonds 6. Measure and record O-H and H-bond lengths 7. Comment on values. 8. Compare the O-H bond lengths for acetic acid and acetic acid dimer and comment

Fechter CHM202 Spring 2009