Speculation: Luminescence from photosynthetic materials and chemiluminescence (CIEEL) indicate the potential of extracting energy from isothermal systems

Original English abstract Original Japanese abstract

(Abstract of the 54th Annual Meeting of the Japanese Society of Plant Physiologists
* 30 Nov., 2012: Submitted to the Organizing Committee of the 54th Annual Meeting of the Japanese Society of Plant Physiologists
*14 March, 2013: Open to the public access (by the members of the Society)
* 20-22 March, 2013: Presented at the 54th Annual Meeting, (Okayama))




Hidehiro, SAKURAI ([email protected])

Guest Research Fellow, Research Institute for Photobiological Hydrogen Production, Kanagawa University
Emeritus Professor, Research Institute for Science and Engineering, Waseda University







Part I　Maxwell’s demon

In a thought experiment, J. C. Maxwell (1871) created a demon who is able to extract energy from an isothermal system for work (Slide 1-3), which seems to violate the second law of thermodynamics. Later, Szilárd argued that the demon does not violate the second law, on the ground of the information entropy.

However, the following observations 1) and 2) indicate that it may be possible to extract energy from an isothermal system without the participation of the demon.
1) Delayed light emission in the subsequent dark from pre-illuminated photosynthetic materials (Strehler et al. (1951), J Gen Physiol 34: 809). After illumination, some transiently reduced component (A-) is produced on the acceptor side and some oxidized component (D+) on the donor side. Some of A- combine with D+ with light emission (the light route) and the others generate heat without light emission (the dark route).
2) Chemically initiated electron exchange luminescence (CIEEL) by dioxetanes (ONeil al. (1970), JACS 92:6553). In some of the above cases, the light energy of the light routes exceeds the heat generated by the dark routes. The extra energy for light emission should come from the thermal energy of the surrounding medium.




Part II　Explanation
The possibility of extracting energy from a isothermal system without the intervention of a demon

In a certain chemical reaction, for example, given its activation energy at 300 K to be 50 and 75 kJ mol-1 in the presence and absence of a catalyst respectively, the fractions of the molecule with equal to or larger than the activation energy at a time are extremely small, only one out of 5 x 108 and 1.2 x 1015 molecules respectively (Boltzmann’s distribution). However, due to frequent energy exchange between molecules, many chemical reactions including biochemical ones proceed at measureable rates without the intervention of an intelligent being (demon) that chooses high-energy molecules.

Because chemical reactions are reversible in principle, we can’t extract energy from an isothermal system. However, in chemical reactions accompanied by photochemical reactions as exemplified in 1) and 2) below, it seems that we will be able to extract energy from an isothermal system without a Maxwell’s demon.



1) Delayed light emission in the subsequent dark from pre-illuminated photosynthetic materials

(Strehler et al. (1951), J Gen Physiol 34: 809).

In living photosynthetic organisms and photochemical reaction center preparations thereof, some reduced acceptors (A-) are transiently formed on the acceptor side, and oxidized donors (D+) on the donor side respectively. In the following dark, some portions of A- and D+ recombine by emitting light (light route), and others without emitting light to return to the ground state just generating heat (dark route) (For example, see: Fig. 4 in Arata and Parson (1981), Fig. 2 in Vaas (2003)).

In the light route, the energy of light is larger than the redox energy of the A- and D+, couple, and the extra energy for light emission should come from the thermal energy in the surrounding medium.



2) Chemically initiated electron exchange luminescence (CIEEL) by dioxetanes

Some organic chemicals such as firefly liciferin decompose by emitting light. In some of dioxetanes that are assumed to decompose probably through CIEEL, thermodynamic energy parameters are determined or estimated (ONeil al. (1970), Adam et al. (1992)). In some of dioxetanes, the light energy of the light routes exceeds the heat generated by the dark routes (For example, see Fig. 1 and Scheme 2, in Matsumoto (2004)). The extra energy for light emission should come from the thermal energy of the surrounding medium.




References



(Open to Kanagawa University home page access, 21 June, 2013)
(Open to Waseda University home page access, 28 October, 2013)