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The fast diffusion of proton and hydroxyl ions


Damned fast reactions
Manfred Eigen Scientist
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We had already worked out a theory, and this was in particular a theory on sound absorption. So that means the perturbing parameter was an oscillating parameter, it's a pressure wave. And it had to be... the theory followed an idea of Meixner, Joseph Meixner, you have to do similar thing as in a optical spectrum of coupled oscillators. You have to look for the normal modes, but this might be too difficult now to explain, and we worked out such a theory of normal modes, that means it involved some co-ordinate transformations to main axis and so on. So it was not a trivial theory.

[Q] It was a solid theoretical basis.

Yes, we had the theory and I asked Tamm and Kurtze to measure very clear chemical equilibrium which was well known, that of ammonia in solution, you know, NH3, the ammonia plus the water molecules, plus H2O, gives you an ammonium ion, NH4+, plus an OH- ion, this was a well known equilibrium... mean use a volume change and the pressure dependants, and I calculated the diffusion controlled reaction. Debye had worked on that and that's how I later became very well acquainted to Peter Debye. But we could calculate everything, and they did the measurement and within a few percent they found the data which I had calculated there. So it was a well established method and I said, but with sound it sometimes difficult to get a large time range because it's a resonance method, you have to use several frequencies. If you go to low frequencies you need very large volumes because the wavelengths of the sound becomes very large. That all is better with electrical waves and even we developed a temperature jump.

So I went to Bonhoeffer and told him, 'Look, I know the principle, know how to study fast reactions, and I will do so'. And we did this, within a year we had the first results, and in 1954 it happened that the Faraday Society had a meeting with the title The Study of Fast Reactions.

[Q] Where?

That was in Birmingham. So I was for my first time was invited to England, was first invited to Cambridge to meet later friends, Ronald Norrish and George Porter, we got a Nobel Prize together in 1967 then, and we went together from Cambridge to Birmingham. And there it happened that I talked about my methods. One of the first speakers was Ronnie Bell. Ronnie Bell has written a famous book on the proton in chemistry... and Ronnie called his reactions 'fast reactions'. So the next speaker was Roughton. Roughton said, 'Since my predecessor has called his reactions fast...' he went down to milliseconds as I told you, 'I must call my reactions "very fast" reactions'. And then came Ronald Norrish with a flash photolysis which went down to the microsecond, and said, 'So I'll have to talk about "extremely fast" reactions'.

Then I had to give my lecture and say, 'I'm sorry, my English is not good enough. The reactions which Professor Norrish talked about, he called extremely fast, but these are the slowest among my data. I have to go down to 10-9 seconds, how should I call them?' 'Oh', they said, 'call them damned fast reactions or goddamn fast reactions'. So that was the origin of it. And that was a little bit sensational at the meeting, that suddenly one could get down to that word, and the year afterwards we measured the rate of the neutralisation reaction, proton plus hydroxyl ion with water, which turned out to be the fastest reactions in solution.

Nobel Prize winning German biophysical chemist, Manfred Eigen (1927-2019), was best known for his work on fast chemical reactions and his development of ways to accurately measure these reactions down to the nearest billionth of a second. He published over 100 papers with topics ranging from hydrogen bridges of nucleic acids to the storage of information in the central nervous system.

Listeners: Ruthild Winkler-Oswatitch

Ruthild Winkler-Oswatitsch is the eldest daughter of the Austrian physicist Klaus Osatitsch, an internationally renowned expert in gas dynamics, and his wife Hedwig Oswatitsch-Klabinus. She was born in the German university town of Göttingen where her father worked at the Kaiser Wilhelm Institute of Aerodynamics under Ludwig Prandtl. After World War II she was educated in Stockholm, Sweden, where her father was then a research scientist and lecturer at the Royal Institute of Technology.

In 1961 Ruthild Winkler-Oswatitsch enrolled in Chemistry at the Technical University of Vienna where she received her PhD in 1969 with a dissertation on "Fast complex reactions of alkali ions with biological membrane carriers". The experimental work for her thesis was carried out at the Max Planck Institute for Physical Chemistry in Göttingen under Manfred Eigen.

From 1971 to the present Ruthild Winkler-Oswatitsch has been working as a research scientist at the Max Planck Institute in Göttingen in the Department of Chemical Kinetics which is headed by Manfred Eigen. Her interest was first focused on an application of relaxation techniques to the study of fast biological reactions. Thereafter, she engaged in theoretical studies on molecular evolution and developed game models for representing the underlying chemical proceses. Together with Manfred Eigen she wrote the widely noted book, "Laws of the Game" (Alfred A. Knopf Inc. 1981 and Princeton University Press, 1993). Her more recent studies were concerned with comparative sequence analysis of nucleic acids in order to find out the age of the genetic code and the time course of the early evolution of life. For the last decade she has been successfully establishing industrial applications in the field of evolutionary biotechnology.

Tags: sound absorption, optical spectrum, coupled oscillators, Faraday Society, fast reactions, flash photolysis, The Proton in Chemistry, Joseph Meixner, Peter Joseph William Debye, Karl-Friedrich Bonhoeffer, George Hornidge Porter, Baron Porter of Luddenham, Ronald George Wreyford Norrish, Ronald Percy "Ronnie" Bell, Francis John Worsley Roughton

Duration: 4 minutes, 34 seconds

Date story recorded: July 1997

Date story went live: 24 January 2008