Experiment 4: Affect of Molecular Structure on pKa of Ground and Excited States of 2-naphthol Chelsie Binda CH 333 8 April 2014

Abstract:

Introduction: The physical and chemical properties of a molecule, such as charge distribution, geometry, electron affinity, ionization potential, and chemical reactivity, are very much dependent upon the electronic structure of the molecule. This being said, if the electronic structure of the molecule were changed, the physical and chemical properties would also be expected to change. This experiment looks at the pKa of 2-naphthol and Experimental: First, 1 mL of 2-naphthol was added to each of two vials and diluted with 4 mL of HCl in one and NaOH in the other. Then, the pH of each was recorded using a pH meter, a UV-Vis spectrum of each was obtained, and a fluorescence spectrum of each was provided. Once this was completed, 1 mL of the 2-naphthol solution was diluted with NH4OH:NH4Cl mixtures. Nine solutions varying in concentrations from 3:1 to 1:3 ratios were prepared. The volumes used to prepare these solutions can be found in Table 1. Finally, a UV-vis spectrum, as well as the pH, was obtained for each solution. Table 1. Volumes of solutions used to prepare diluted solutions of 2-napthol with NH4OH:NH4Cl mixtures Solution # Ratio NH4OH NH4Cl (mL) 2-naphthol Total Volume (mL) (mL) (mL) 1 1:1 2 2 1 5 2 1:1.5 1.6 2.4 1 5 3 1:2 1.33 2.66 1 5 4 1:2.5 1.14 2.86 1 5 5 1:3 1 3 1 5 6 3:1 3 1 1 5 7 2.5:1 2.86 1.14 1 5 8 2:1 2.66 1.33 1 5 9 1.5:1 2.4 1.6 1 5 Results: The pH of each solution was determined using a pH meter. These values are shown in Table 2. The UV-Vis spectrum of 2-naphthol in NaOH and HCl, Figure 1, was then interpreted and it was determined that the acid form is blue shifted compared to the base form, which means that the acid will require more energy to reach its excited state. Equation 1 and the pKa values of the buffered solutions were used to construct the graph of AJHSFIOJH shown in Figure 2. The value for AArO- is the wavelength maximum absorbance where the absorbance of the acid is zero, and A is buffered solutions Figure 3. Equation 1 ( ) Then, the pKa was determined from both the x and y-intercepts to be 8.3028 or 10.97 respectively. After this, the pKa of the excited state molecule (pKa*) was determined using Equation 2 shown below where pKa is the average of the two

calculated pKa values, 9.2, h is Plancks constant, c is the speed of light, R is the gas ) is the energy difference between constant, T is temperature, and ( the transition energies of the acid and base forms. If the average of the two pKa values had not been used, the higher value, 10.97 would have been used because this value was obtained by assuming is equal to 0. This results in the equation pH=pKa and removes any error that may have resulted from the A terms. When using the average pKa, pKa* was determined to be 5.80 when using the UV-Vis spectra and 0.360 when using the fluorescence spectra, Figure 4. Equation 2 Solution 2-naphthol in NaOH 2-naphthol in HCl 1 2 3 4 5 6 7 8 9 pH 13.47 0.83 9.55 9.25 9.15 9.02 9.00 9.93 9.91 9.77 9.64 ( )

Discussion: From this experiment it was determined that the pKa of 2-naphthol is in between 8.3 and 10.1. The literature value for the pKa of this substance as according to Wikipedia is 9.51. If the experimental values are averaged, a pKa value of 9.2 is obtained, which provides a percent error of 3% which is low compared to a percent yield of 13% for a pKa of 8.3 and 6% for a pKa of 10.1. Using the ground state pKa the excited state pKa was determined to be between 5.8 and 0.36 producing an average of 3.08. However, no literature values can be found for comparison. On the other hand, this information tells us that the excited state acid is a stronger acid than the ground state acid because the excited state molecule corresponds with a smaller pKa. The isosbestic point is the wavelength at which the spectra of two solutions cross because they have the same molar absorptivity. The isosbestic points of the UV-Vis spectra and the fluorescence spectra are labeled. Using the knowledge obtained in this lab, the acidic properties of ground state and excited state 2naphthoic acid can be predicted. I would expect 2-naphthoic acid to be a stronger acid than 2-naphthol in the ground state and excited state because of the electron density in the carbonyl group in the molecule. The double bond to the oxygen will pull more electrons away from the OH group on the molecule allowing the proton to be lost more readily. Therefore it will be the stronger acid. References: