Tuesday, August 9, 2011

Hydronium Ions in Fermentation

Ethanol or ethyl alcohol (C2H5OH) can be produced from glucose (C6H12O6) by fermentation using an enzyme as a catalyst:
2 C2H5OH + 2 CO2
Chemists are very interested in studying this reaction because it has the potential to convert the sugars in woody biomass into alcohols which can be used as a fuel in place of non-renewable fuels obtained from petroleum. It is known that the enzyme in yeast which is commonly used in the production of ethanol loses its effectiveness when the pH of the reaction mixture is lowered.

In aqueous solutions, as soon as protons (H+) are released by an acidic species they bond with water molecules (H2O) to form hydronium ions (H3O+) :

H+ + H2O → H3O+

and pH is a measure of the hydronium ion concentration:
pH = -log[H3O+]
although we often think of this as being the same as a measure of the proton concentration:
pH = -log[H+]
since we reasonably expect all the protons to have reacted with water molecules to form hydronium ions.

Los Alamos National Laboratory scientists substituted hydrogen in their enzyme samples with deuterium, an isotope of hydrogen (hydrogen-2). Unlike hydrogen-1 atoms, deuterium atoms provide a clear signal when bombarded with neutrons so they are visible to X-rays, this fact can be used to study the enzyme catalyzed process of fermentation.

The scientists found that as the pH fell below 6, hydronium ions (H3O+) that are vitally important in the conversion of the sugar molecule into its fermentable form suddenly became dehydrated.
H3O+ → H2O + H+

The space in the enzyme occupied by the relatively large hydronium ion collapsed into a tiny volume occupied by the remaining proton (H+). This spatial change in the molecular structure prevented the sugar from being attacked by the enzyme.

The observed phenomenon provided an answer about why pH plays such an important role in the process and renders the enzyme inactive under acidic conditions. More important, it definitively illustrated that the hydronium ion plays a key role in the transport of protons in these types of biochemical systems.

Andrey Y. Kovalevsky, B. L. Hanson, S. A. Mason, T. Yoshida, S. Z. Fisher, M. Mustyakimov, V. T. Forsyth, M. P. Blakeley, D. A. Keen, Paul Langan. Identification of the Elusive Hydronium Ion Exchanging Roles with a Proton in an Enzyme at Lower pH Values. Angewandte Chemie International Edition, 2011; 50 (33): 7520 DOI: 10.1002/anie.201101753

Further Reading:
Mass-Mole Calculations
Gas Volume Calculations
Molarity Calculations
Yield Calculations
pH Calculations

Study Questions:
  1. A Chemist undertook a fermentation experiment using 10g of glucose dissolved in 1L of water.
    • How many moles of glucose were present in the solution?
    • What was the concentration of the initial glucose solution?
    • What is the maximum yield of ethanol that could be produced from this reaction mixture?
    • If the actual yield of ethanol was 4% by mass, how many moles of ethanol was produced?
    • If the actual yield of ethanol was 4% by mass at 25oC, what volume of carbon dioxide gas was be produced?
  2. Assuming the fermentation of glucose reaction occurs at a constant temperature of 25oC
    • Calculate the concentration of hydronium ions present in a reaction mixture with a pH of 6.
    • Calculate the concentration of hydroxide ions present in a solution with pH of 6
    • Calculate the pOH of a solution with a pH of 6.
  3. What is meant by the term catalyst?
  4. What is meant by the term enzyme?
  5. Explain why the hydronium ion is larger than the hydrogen ion.
  6. Would the hydronium ion be larger or smaller than a water molecule? Explain your answer.
  7. How would you define the term isotope?
  8. Explain why deuterium is considered to be an isotope of hydrogen.

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