Abstract

The purpose of this experiment is to determine the equilibrium composition, equilibrium

constant (Kc) and the standard free energy differences (ΔG) of three keto-enol mixtures by

examining the NMR (nuclear magnetic resonance) spectrum obtained from the analyzed

solutions. From the obtained data, it was determined that the enolate ions tend to be more stable

under non-polar solvents like CCl4, while the ketone form tends to be more predominant in polar

solvents. Steric hindrance also tends to be a factor between the interconversion between enol and

keto forms since bulky di-Ketones favor the ketone form over the enol form.

Theory

The chemical equilibrium between Keto form (from a ketone or aldehyde), and the enol

form (an alcohol), is known as Keto-Enol tautomerism. These two forms coexist in equilibrium

with the Keto form being the predominant one. The interconversion between both forms involves

the movement of a hydrogen atom and a pair of bonding electrons. Proton NMR can be utilized

to distinguish each keto-enol isomer since the migration of the proton will experience a different

chemical environment, thus different peaks can be seen in the NMR for each Keto-Enol

tautomer.

Nuclear Magnetic Resonance is one of the major techniques for obtaining information

about a system at the molecular level. NMR uses the excitation of the atomic nuclei into different

transitions to obtain information about the structure, utilizing mainly the electrons, surrounding

the nucleus. These excitations are brought on through a strong magnetic field generated through

a permanent magnet alongside electromagnets located within the NMR machine

 Any elementary particle that has a charge and a spin will have a magnetic moment, thus,

both electrons and protons have this characteristic. When a strong magnetic field is applied to

these elementary particles, some will align along the direction of the magnetic field while others

will align opposite to the direction of the magnetic field. This change in alignment requires

energy to happen, especially when particles align opposite to the magnetic field. Due to this

phenomenon, a spin state will have different allowed transitions with different energies

associated with each transition. The energy spacing between each allowed level can be calculated

using the formula:

E=hv,

where h is Planck’s constant and v is the frequency of the radiation being used.

The NMR spectrum of organic compounds tends to be complicated, since many compounds will

show many multiplets, and these multiplets arise from spin-spin splitting patterns when the

magnetic moment of one proton interacts with another nearby nucleus causing an energy shift up

or down depending on the relative orientations of the two moments. These interactions are

characterized by the coupling constant, J, and the intensity of each multiplets is determined by

the relative population of each transition.

B-di-Ketones and B-Keto-Esters have intramolecular hydrogen bonding and conjugation that

increases the stability of the enol form, and thus the equilibrium between enol and keto forms

can be shifted slightly more towards the enol tautomer. Since the chemical environments are

different for both forms, a distinct NMR spectra is obtained for both tautomer and they can be

used to determine the equilibrium constant for the keto to enol conversion.

𝑒𝑛𝑜𝑙
𝐾𝑐 = 𝑘𝑒𝑡𝑜 (1)
From the calculated equilibrium constant and the use of the following equation

∆𝐺 = −𝑅𝑇𝑙𝑛𝐾𝑐 (2)

The change in Gibbs free energy can be calculated, where R is the gas constant and T is the

temperature in kelvin.

Procedure

In this experiment two solvent solutions were prepared in 10 mL volumetric flask using a

five percent by volume of TMS and carbon tetrachloride labeled solvent A, and a five percent by

volume TMS and methanol labeled solvent B. Utilizing these two solvents, three different

solutions were prepared: solution 1 was prepared in a 10 mL volumetric flask composing of 0.20

mole fraction of acetylacetone in solvent A. Solution 2 had a composition of 0.20 mole fraction

of acetylacetone in solvent B. Solution 3 was composed of 0.20 mole fraction of ethyl

acetoacetate in solvent A. When calculating of the mole fraction of the corresponding solutions,

the five percent of TMS added were omitted. Once all the solutions were prepared accordingly,

they were taken to the NMR working station for analysis.

Before the analysis of the solutions commenced, the NMR tubes that were used were

tested to make sure they spin when placed inside the apparatus. Once the NMR tubes were

checked, each individual solution was analyzed per the provided instructions using the correct

program. Each obtained NMR spectrum was also individually analyzed and integrated to the

according keto or enol peaks utilizing the NUTS program.

Discussion

For the completed experiment, the NMR spectrums for solutions 1-3 (spectrum 3-5) and

the solvents A and B (spectrum 1-2) were analyzed for specific structural features. When

analyzing solvent A (spectra 1), only one peak could be observed which belonged to the TMS

indicator. This was to be expected since CCl4 does not have any NMR active protons. For

solvent B, three peaks were observed: one belonged to the TMS indicator, while the other peaks

belong to the -OH and -CH3 protons in the methanol molecule. For solution 1 (0.20 mole fraction

of acetylacetone in solvent A)(spectrum 3) four peaks could be observed, two of which belong to

the keto form (2.178 and 3.486 PPM) and two which belong to the enol form (2.013 and 5.469

PPM). Utilizing the data, the Kc for the keto-enol equilibrium was calculated to a value of

6.56 1
Kc= .57 = 11.50 for the -CH3(enol)/-CH3(keto) peaks, and Kc=(0.07) = 14.28 for the =CH

(enol)/-CH2(Keto). An average value of 12.89 for Kc was calculated and an average change of

free energy for the Keto-Enol tautomerism was calculated using equation 2, ΔG= -6.33 Kj/mol.

For solution 2 (0.20 mole fraction of acetylacetone in solvent B)(spectrum 4), the Kc was

calculated using the respective keto and enol peaks as well. For the -CH3 (enol)/-CH3(Keto) a
0.39
value of Kc= 0.11 = 3.54 and for the =CH (Enol)/-CH2(Keto) the Kc was calculated to a value of

0.08
Kc=0.03 = 2.66. An average value of Kc was calculated to 3.1 which yielded an average ΔG = -

2.8 Kj/mol.

For solution 3 (0.20 mole fraction ethyl acetoacetate in solvent A)(spectrum 5), the kc was

calculated utilizing the respective keto-enol peaks; the -CH3(enol)/CH3(keto) ratio yielded a Kc=

0.94 and the =CH(enol)/CH2 (keto) ratio gave a Kc=1.01 for an average Kc = .98 and an average

ΔG=-0.05 Kj/mol.
 From the calculated data for both equilibrium constant and change in free energy, it can

be observed that the enol form is more predominant in a non-polar solvent since the Kc and

change in free energy were larger in the CCl4 solvent than in the methanol solvent. This shows

that the keto form tends be more polar, thus liking a polar solvent will be favored though more

H-bonding. When comparing solution 1 and solution 3, the steric effects in the keto-enol

equilibrium were apparent. Solution 1 had a larger amount of enolate ions when compared to the

amount present in solution 3. This determined that the bulkiness of ethyl acetoacetate vs

acetylacetone can cause a difference in the amount of H-bonding stabilization obtained from the

enolate ions thus acetylacetone contains a higher concentration of enol when compared to ethyl

acetoacetate.

Conclusion

In the concluded experiment, the equilibrium constant between enol and keto

interconversion was determined from the use of NMR data obtained through the analysis of

certain solutions. In each solution, different factors like the polarity of solvent and bulkiness of

the di-Ketone, were used to determine if these factors changed the amount of keto-enol

tautomerism. From the collected data, it was assessed that polar solvents tend to favor the keto

form while non-polar solvents favor the enol form, and that bulky di-Ketones favor the ketone

form instead of the enol form. The equilibrium constants and change in Gibbs free energy were

calculated to conclude these observations. Overall this experiment was successful and was

concluded with no problems.

References
 Garland, C. W., Nibler, J. W., & Shoemaker, D. P. (2009). Experiments in physical

chemistry (8th ed.). Boston: McGraw-Hill Higher Education

AIST:Spectral Database for Organic Compounds,SDBS. (n.d.), from

http://sdbs.db.aist.go.jp/sdbs/cgi-bin/direct_frame_top.cgi