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Superacids and the Hammett Acidity Function

1932
  • James Bryant Conant
  • George A. Olah
  • Louis Plack Hammett
Chemist measuring superacid solutions in an organic chemistry laboratory.

(generated image for illustration only)

A superacid is an acid with an acidity greater than that of 100% pure sulfuric acid. The conventional pH scale is inadequate for these media. Instead, their acidity is measured using the Hammett acidity function, \(H_0\). This function is based on the protonation of weak indicator bases and is defined as \(H_0 = pK_{BH^+} – \log\left(\frac{[BH^+]}{[B]}}\right)\).

The Hammett acidity function, \(H_0\), extends the concept of pH to highly concentrated or non-aqueous acidic solutions where the activity of the proton is no longer simply related to its concentration. It measures the medium’s ability to protonate a neutral weak base ‘B’. The value of \(H_0\) is determined experimentally using a series of weak bases with overlapping \(pK_{BH^+}\) values, typically aromatic amines, and measuring the ratio of their protonated (\(BH^+\)) to unprotonated (\(B\)) forms via UV-visible spectroscopy. For dilute aqueous solutions, \(H_0\) is approximately equal to pH, but it diverges significantly in concentrated acids, taking on large negative values. For example, 100% \(H_2SO_4\) has an \(H_0\) of -12.

George Olah’s work with superacids, such as ‘Magic Acid’ (\(FSO_3H-SbF_5\)), which has an \(H_0\) around -23, was revolutionary. It allowed for the preparation and direct observation of stable carbocations, which were previously only considered transient intermediates. This opened up new frontiers in physical organic chemistry and earned him the Nobel Prize in Chemistry in 1994.

UNESCO Nomenclature: 2208
– Organic chemistry

Type

Abstract System

Disruption

Substantial

Usage

Niche/Specialized

Precursors

  • Brønsted–Lowry acid–base theory
  • Lewis acid theory
  • understanding of reaction mechanisms and intermediates
  • development of UV-visible spectroscopy

Applications

  • catalysis in the petrochemical industry (e.g., isomerization of alkanes)
  • synthesis of carbocations for spectroscopic study
  • protonation of extremely weak bases
  • organic synthesis reactions requiring strong protonation
  • high-octane gasoline production

Patents:

NA

Potential Innovations Ideas

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Related to: superacid, Hammett acidity function, H0, strong acid, carbocation, George Olah, magic acid, physical organic chemistry, catalysis, non-aqueous.

Historical Context

Superacids and the Hammett Acidity Function

1930
1930
1931
1932
1936-01-01
1938
1940
1930
1930
1931
1932
1933
1937
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1947

(if date is unknown or not relevant, e.g. "fluid mechanics", a rounded estimation of its notable emergence is provided)

Related Invention, Innovation & Technical Principles

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