The hydroxyl radical is the dominant oxidizing chemical in Earth’s atmosphere. It is also the most common and most active free radical present in human and other animal tissue, yet it is contained in chemically pure water.
A radical is a molecular ion, a group of two or more atoms bonded together into a single unit that possesses an electric charge.
A free radical is usually negatively charged and looking for a “free” positively charged ion to bond with by stealing or borrowing a proton in a process known as oxidation.
“Hydroxyl” refers to a chemical grouping in which oxygen and hydrogen are covalently bonded into a single negatively charged entity, or OH. Chemically speaking the hydroxyl radical is a hydroxide ion, and it frequently bonds with positively charged metal ions, for example sodium hydroxide (NaOH), commonly known as lye.
The most common place to find a hydroxyl radical is in a water molecule. Water might also be thought of as “hydrogen hydroxide” because the hydroxyl radical preferentially bonds with a positive hydrogen ion to form a water molecule (HOH).
This is because a reaction occurs when an acid and an alkali react chemically forming water and a salt.
The reaction between acid and alkali is actually a unique type of oxidation-reduction reaction that is continually occurring in liquid water at the molecular level.
Although water molecules are exceptionally stable, in the liquid a small fraction spontaneously dissociate into positive hydrogen ions and negative hydroxide ions, maintaining a dynamic equilibrium as equal numbers of individual ions recombine to form water molecules.
This dissociation happens as water molecules bounce around with thermal energy at a thousand miles per hour forming, breaking, and reforming incomplete nanoscale ice crystals in the liquid state. Both of these processes occur billions of time every second.
The high rate at which hydroxide ions combine makes them a particularly aggressive oxidant.
In neutral (neither acidic nor alkaline) water
at pH 7 the fraction of dissociated molecules is
10 to the minus seventh, meaning that 1 out of every 10 million molecules is split into their component hydrogen and hydroxide ions at any instant.
The hydroxyl radical exists as a free radical in the atmosphere where it is the primary removal mechanism for methane and volatile organic carbon compounds, or VOCs. It behaves like a typical gas molecule until it comes in contact with an organic molecule, virtually all of which contain hydrogen atoms bonded to carbon atoms.
Because the hydroxyl radical’s activity is so vigorous for hydrogen, it plucks hydrogen atoms from their bonds with carbon atoms, leading to their ultimate destruction and creating a water molecule.
The hydroxyl radical is neutralized when it combines with the hydrogen ion to become a water molecule. To keep the atmosphere supplied with hydroxyl radicals there must be processes that generate new radicals.
This is mostly by photo dissociation, which occurs either by water molecules being directly split by ultraviolet radiation or by certain wavelengths of incoming sunlight that break apart ozone molecules to release an “excited” oxygen atom that bonds with a water molecule, which then splits into two hydroxyl radicals.
This is yet another example of the intricacies and complexities of water and the multiple roles it plays in supporting life and the global ecosystem necessary to maintain it.
Richard Brill is a retired professor of science at Honolulu Community College. His column runs on the first and third Fridays of the month. Email questions and comments to brill@hawaii.edu.