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Updated: Jun 1, 2026

Determination of the Gas-phase Acidities of Oligopeptides
Published on: June 24, 2013
Calculations of pKa of superacids in 1,2-dichloroethane
Aleksander Trummal1, Alar Rummel, Endel Lippmaa
1National Institute of Chemical Physics and Biophysics, 10 Rävala Blvd., Tallinn 10143, Estonia. aleksander.trummal@kbfi.ee
Abstract:
Acidity calculations for some CH and NH superacids in 1,2-dichloroethane (DCE) were carried out using SMD and COSMO-RS continuum solvation models. After comparing the results of calculations with respective experimental pK(a) values it was found that the performance of SMD/M05-2X/6-31G* method is characterized by the mean unsigned error (MUE) of 0.5 pK(a) units and the slope of regression line of 0.915. The similar SMD/B3LYP/6-31G* approach was slightly less successful. The strong correlation over entire data set is confirmed by R(2) values of 0.990 and 0.984 for M05-2X and B3LYP functionals, respectively. The COSMO-RS method, while providing the value of the linear regression line slope similar to the corresponding values from SMD approach, characterized by rather loose correlation (R(2) = 0.823, MUE = 1.7 pK(a) units) between calculated and experimental pK(a) values in DCE solution.
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Acidity of 1-Alkynes
The acidic strength of hydrocarbons follows the order: Alkynes > Alkenes > Alkanes. The strength of an acid is commonly expressed in units of pKa — the lower the pKa, the stronger the acid. Among the hydrocarbons, terminal alkynes have lower pKa values and are, therefore, more acidic. For example, the pKa values for ethane, ethene, and acetylene are 51, 44, and 25, respectively, as shown here.
Acid and Bases: Ka, pKa, and Relative Strengths
Weak Base Solutions
Solvating Effects
Titration Calculations: Weak Acid - Strong Base
For the titration of 25.00 mL of 0.100 M CH3CO2H with 0.100 M NaOH, the reaction can be represented as:
Acidity of Carboxylic Acids

