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Ionization Constants of DL-2-Aminobutyric Acid and DL-Norvaline Under Hydrothermal Conditions by UV–Visible Spectroscopy

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Abstract

The first and second ionization constants for the amino acids DL-2-aminobutyric acid (DL-2-aminobutanoic acid) and DL-norvaline (DL-2-aminopentanoic acid) were determined under hydrothermal conditions, from 175 to 275 °C at 10 MPa, using thermally-stable colorimetric pH indicators (acridine, 4-nitrophenol and 2-naphthoic acid). The measurements were carried out by UV–visible spectroscopy using a high-temperature, high-pressure platinum flow cell with sapphire windows, which minimized the effects of thermal decomposition. The results were combined with literature values from titration calorimetry at 25–130 °C to yield an extended van’t Hoff model for the temperature dependence of the ionization constants for the carboxylic acid and ammonium groups, \( K_{\text{a,COOH}} \) and \( K_{{{\text{a,NH}}_{3}^{ + } }} \), over the entire temperature range. The experimental results for the second ionization constant \( K_{{{\text{a,NH}}_{3}^{ + } }} \) at elevated temperatures are consistent with the predictions from the Yezdimer–Sedlbauer–Wood functional group additivity model, but for the first ionization constant \( K_{\text{a,COOH}} \) are not. This suggests that the group contribution parameters for the standard partial molar heat capacity of the carboxylic acid group are in error, or that nearest neighbor interactions between the –COOH and \( - {\text{NH}}_{3}^{ + } \) groups cause a breakdown in the functional group additivity relationship.

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Acknowledgements

This research was supported by the National Science and Engineering Research Council of Canada (NSERC), and by the “Apoyo a Doctorados Nacionales 2004” program from Colciencias, which provided a Ph.D. travel scholarship to D. E. Nieto Roca. We are grateful to Dr. Liliana Trevani and Dr. Jenny Cox who provided technical advice, scientific input and encouragement. We are also grateful to Mr. Ian Renaud and Mr. Case Gielen of the electronics shop and machine shop in the College of Physical and Engineering Science at the University of Guelph for their very considerable expertise in constructing and maintaining the UV–visible flow cell system. The functional group additivity calculations were carried out by Prof. Dr. Josef Sedlbauer at the University of Liberec in the Czech Republic, who also provided insightful advice and encouragement.

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  1. Departamento de Química, Facultad de Ciencias, Universidad Nacional de Colombia, Calle 44 # 45-67 Bloque B9, Bogotá, Colombia

    Daniel E. Nieto Roca & Carmen M. Romero

  2. Department of Chemistry, University of Guelph, Guelph, ON, N1G 2W1, Canada

    Peter R. Tremaine

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  1. Daniel E. Nieto Roca
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Appendix: Ionization Constant for 2-Naphthoic acid

Appendix: Ionization Constant for 2-Naphthoic acid

As stated in the text, the temperature dependence of the ionization constant of 2-naphthoic acid was recalculated. Table 8 shows the results for the ionization constant of DL-2-aminobutyric acid at 200 °C obtained in this study with the two indicators. The value obtained with 4-nitrophenol was used as the true value for the constant at this temperature. The new ionization constant for 2-naphthoic acid was found by rearranging Eq. 21 to

$$ K_{\text{HInd}} = K_{{{\text{a,NH}}_{ 3}^{ + } }} \frac{{m_{{{\text{HA}}^{ \pm } }} }}{{m_{{{\text{A}}^{ - } }} }} {\cdot} \frac{{m_{\text{Ind}} }}{{m_{\text{HInd}} }} = \frac{{K_{{{\text{a,NH}}_{ 3}^{ + } }} }}{{\left( {\frac{{m_{{{\text{A}}^{ - } }} }}{{m_{{{\text{HA}}^{{{ \pm }}} }} }}} \right)\left( {\frac{{m_{\text{HInd}} }}{{m_{\text{Ind}} }}} \right)}} $$
(A1)

with the values of indicator and buffer ratios obtained for the spectra of 2-naphthoic acid at 200 °C. These results are listed in Table 12.

Table 12 Experimental values of 2-naphthoic acid, \( {\text{p}}K_{{ 2 {\text{ - NaphCOOH}}}} \), at \( \left( {200 \pm 0.1} \right) \, ^\circ {\text{C}} \)
Full size table

The extended van’t Hoff model was used to establish the temperature dependence of \( K_{{ 2 {\text{ - NaphCOOH}}}} \). As noted before, this model works well with isocoulombic reactions, where the assumption of small and constant \( \Delta_{\text{r}} C_{p}^{\text{o}} \) is valid. For this reason, the reaction for the ionization of 2-naphthoic acid (Eq. 11) was rewritten as

$$ 2{-} {\text{NaphCOOH}} + {\text{OH}}^{ - } \rightleftharpoons 2 {-} {\text{NaphCOO}}^{ - } + {\text{H}}_{2} {\text{O}} $$
(A2)

where

$$ K_{\text{OH,2 - NaphCOOH}} = \frac{{K_{{ 2 {\text{ - NaphCOOH}}}} }}{{K_{\text{w}} }} = \frac{{m_{\text{Ind}} }}{{m_{\text{HInd}} {\cdot} m_{{{\text{OH}}^{ - } }} }} . $$
(A3)

Results from literature for \( K_{{ 2 {\text{ - NaphCOOH}}}} \) from Briggs et al. [51] and our result for 200 °C were used to calculate \( K_{\text{OH,NaphCOOH}} \), along with data for water from Sweeton et al. [41]. Equation 29 was then fitted to \( K_{\text{OH,NaphCOOH}} \), using \( \Delta_{\text{r}} H_{\text{NaphCOOH}}^{\text{o}} \) and \( \Delta_{\text{r}} H_{\text{W}}^{\text{o}} \) at 25 °C from the same sources, obtaining a value for \( \Delta_{\text{r}} C_{{p\;{\text{NaphCOOH}}}}^{\text{o}} \) of \( - 306.3 \pm 7.3{\text{ J}} {\cdot} {\text{mol}}^{ - 1} {\cdot} {\text{K}}^{ - 1} \). The results from the fitting can be seen in Fig. 12.

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Nieto Roca, D.E., Romero, C.M. & Tremaine, P.R. Ionization Constants of DL-2-Aminobutyric Acid and DL-Norvaline Under Hydrothermal Conditions by UV–Visible Spectroscopy. J Solution Chem 46, 388–423 (2017). https://doi.org/10.1007/s10953-017-0569-z

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