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Infrared characteristic radiation of water condensation and freezing in connection with atmospheric phenomena
Earth-Science Reviews 101 (2010) 24–28
Contents lists available at ScienceDirect
Earth-Science Reviews j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e a r s c i r ev
Infrared characteristic radiation of water condensation and freezing in connection with atmospheric phenomena Vitali A. Tatartchenko Saint-Gobain Crystals, France
a r t i c l e
i n f o
Article history: Received 1 June 2008 Accepted 16 March 2010 Available online 28 March 2010 Keywords: First order phase transitions of water Condensation and crystallization Infrared radiation Atmospheric phenomena Formation of hail Jupiter Infrared laser
a b s t r a c t This paper considers the emission of infrared characteristic radiation during the first order phase transitions of water (condensation and crystallization). Experimental results are analyzed in terms of their correspondence to the theoretical models. These models are based on the assumption that the particle's (atom, molecule, or cluster) transition from the higher energetic level (vapor or liquid) to a lower one (liquid or crystal) produces an emission of one or more photons. The energy of these photons depends on the latent energy of the phase transition and the character of bonds formed by the particle in the new phase. Based on experimental data, the author proposes a model explaining the appearance of a window of transparency for the characteristic radiation in the substances when first order phase transitions take place. The effect under investigation must play a very important role in atmospheric phenomena: it is one of the sources of Earth's cooling; formation of hailstorm clouds in the atmosphere is accompanied by intensive characteristic infrared radiation that could be detected for process characterization and meteorological warnings. The effect can be used for atmospheric heat accumulation. Together with the energy of wind, falling water, and solar energy, fog and cloud formation could give us a forth source of ecologically pure energy. Searching for the presence of water in the atmospheres of other planets might also be possible using this technique. Furthermore, this radiation might explain the red color and infrared emission of Jupiter. © 2010 Elsevier B.V. All rights reserved.
Contents 1. Definition of the scope of discussion . . 2. IR radiation accompanying water phase 3. Experimental data discussion . . . . . 4. Conclusions . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . References . . . . . . . . . . . . . . . .
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1. Definition of the scope of discussion In our preceding papers (Tatarchenko, 1979; Tatarchenko and Umarov, 1980; Tatarchenko, 1993; Tatartchenko, 2008; Tatartchenko, 2009; Umarov and Tatarchenko, 1984) and in their references, evidence of infrared characteristic radiation (IRCR) emission during first order phase transitions was considered. For many substances (among them are water, alkali halides, sapphire, tellurium, germanium, sodium tiosulphate, and some metals), it seemed that the latent heat of melting was radiated directly by the melt crystallization into
E-mail address: [email protected]. 0012-8252/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.earscirev.2010.03.002
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the solid state, while the latent heat of vaporization was radiated directly by the vapor condensing into the liquid state. It is evident, therefore, that first order phase transitions, accompanied by the energy release, are sources of IRCR. Thus, our 46 year old assumption (Tatartchenko, 2008; Tatartchenko, 2009), that the particle's (atom, molecule or cluster) transition from a higher energetic level (vapor or melt) to a lower one (melt or crystal) produces emission of one or more photons, has been proven. In addition, there is definite evidence that photon energies depend on the latent energy of the phase transition and the character of chemical bonds in the new phase. In this paper, we discuss a specific aspect of this effect: the IRCR of the phase transitions of water in connection with atmospheric phenomena. We believe that specialists in different fields could
V.A. Tatartchenko / Earth-Science Reviews 101 (2010) 24–28
25
significantly contribute to the solution of climate problems through further investigations of this phenomenon. Atmospheric radiation is one of the key subjects of atmospheric sciences, linking the fields of chemistry, aerosol, cloud physics, and thermodynamics to global climate and climate change. The Atmospheric Radiation Measurement Program (ARMP), created to resolve scientific uncertainties relating to global climate change, is focused on the crucial role of clouds and their influence on radiative feedback processes in the atmosphere [ARMP 2008 http://www.arm.gov/]. In the framework of ARMP, measurement of the intensity of IRCR accompanying water vapor condensation could provide significant information concerning cloud formation, as well as the energy balance in the atmosphere. Indeed, 40% of the solar energy reaching the Earth's surface is spent on water evaporation. The mechanism under consideration seems to play a very important role in the subsequent redistribution of this energy through condensation and crystallization in atmosphere, including its reemission into space. 2. IR radiation accompanying water phase transitions The data, concerning IR radiation appearance during water phase transitions, may be briefly stated as follows. Nichols and Lamar (1968) developed the idea of an infrared line scan camera. It scans an object simultaneously over three separate spectral ranges and produces an image of the object as a color photograph. The three spectral regions are 0.5–1.0 µm, 3.0–5.5 µm, and 8–14 µm. Each of the infrared spectral ranges is rendered in one of the primary colors—blue, green and red, respectively. As a result, the color of objects in a picture indicates their temperature and also their reflective and emissive properties. The numerous impressive pictures presented by the authors lead to the conclusion that they have indeed found sources of infrared radiation in the range of 8–14 µm in the atmosphere, which can be associated neither with temperature, nor with reflective radiation. These sources correspond to the bottom sides of cumulus clouds with a temperature of −5 °C and to the rising warm air saturated with water vapor. Unfortunately, we could not obtain high quality pictures to reproduce here. Potter and Hoffman (1968) describe experiments that were carried out in an apparatus comprising a vessel with boiling water, a cooled glass surface for vapor condensation, and a sensitive recording system for infrared radiation. An anomalous increase in infrared radiation intensity from the boundary between the glass surface and condensed vapor was observed. This intensity increased with increasing condensation rate. The integrated intensity was four times higher than Plank's radiation in the range of 1–4 µm. Two main emission bands were recorded in the vicinity of 2.10 µm and 1.54 µm (Fig. 1). The intensity of both bands exceeded the background radiation by a factor of ten. A third band with a wavelength of 3.2 µm, not mentioned by the authors, could possibly be detected on the curve of Fig. 1. When observing sonaro-luminescence, Ayad (1971) used a spectrometer with a thermocouple detector and a Lead Sulphide photometer. The peak of emission at wavelength 1.05 µm was detected. A second peak at 0.9 µm, not mentioned by the author, could possibly be recorded on the curve presented in the Ayad's paper. Mestvirishvili et al. (1977) recorded intense infrared radiation during water vapor condensation and water crystallization in a closed chamber. The temperature was lowered by adiabatic expansion. The radiation was observed through a Ge window in the chamber. Systems of filters and mirrors were used to pick out wide desirable IR ranges from the full spectrum. Radiation was detected by a bolometer. This technique allowed the authors to confirm that they had recorded the characteristic radiation for the condensation in the range of 4– 8 µm and for the crystallization in the range of 28–40 µm. The radiation intensity considerably exceeded the background Plank's intensity.
Fig. 1. From Potter and Hoffman (1968) paper. Relative intensity of the phase transition luminescence from water; Iw, intensity from the boiling water; Ibb, intensity from the black body.
In the case of the water vapor discharge laser, the main emission bands are ∼119 µm and 220 µm. On the other hand as it was mentioned by Mestvirishvili and Perelman (1977), few complementary bands have been recorded in its emission spectrum. Four of them, 11.83 µm, 38.1–39.7 µm, 57.8 µm, and 79 µm, which have not been identified, are of interest to us. Presently, a lot of infrared images of the Earth taken from Space exist. As a rule, 6.9–6.7 µm IR radiation of the Earth has been particularly useful for recording water vapor in the Earth's atmosphere. For instance, Hasler et al. (2003) confirm that the NASA orbiting GOES 8 satellite's multi-channel imager produces images of the upper troposphere at the infrared wavelength of 6.7 µm (Fig. 2). Bright regions correspond to high concentrations of water vapor over the oceans, while dark spots are relatively dry areas. 3. Experimental data discussion Evidence of the phenomenon under consideration does not follow from general phase transition concepts. As a rule, high-temperature luminescence has been rejected in favor of the phonon path of energy removal. We think it could be correct when applied to separate particles or to small clusters of a few particles. But in the case of a large number of particles, we believe IRCR has to occur. The phenomenon under consideration, it seems, occurs in the same way as nuclear fission reactions or laser radiation occurs. A critical mass depending on the system geometry is needed for all of these processes to take place. The feasibility of radiative phase transition in terms of quantum electrodynamics (QED) was treated for the first time by Perel'man (1971) and later in few papers including Perel'man and Tatartchenko (2007) and Perel'man and Tatartchenko (2008). Let us consider and refine the main points of two last papers applicable to water phase transition. We accept that when the particle (atom, molecule, or cluster) enters into a new phase, it radiates the latent heat of transition for this particle as one or several quanta which can be thermalized before they leave the substance. The presence of suitable levels of energy is necessary for radiation to occur. It has to be mentioned that the latent heat of condensation as well as the latent
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V.A. Tatartchenko / Earth-Science Reviews 101 (2010) 24–28
C. In the case of complex molecules, transitions with quanta of various frequencies is possible, e.g. for the two-photon case 0
ℏω1 = ℏω + ℏωq
λ0 ⋅λq 120 : = λ1 ≡ λ0 + λq Λ
Or
ð3Þ
More complicated combinations of frequencies can be similarly considered. D. Dimers and more complicated formations, clusters, can be examined as single particles and if the bond energy of atoms/ molecules in them is small enough, wavelengths of radiation for a cluster of M particles with n-photon emission will be of the type: ðMÞ
λn ≈120n = MΛ
Fig. 2. From Hasler et al. (2003) internet site. Earth image at the infrared wavelength of 6.7 μm, recording radiation emitted by water vapor in the upper troposphere. Bright regions correspond to high concentrations of water vapor, while dark spots are relatively dry areas.
heat of crystallization, are not constant; they both change with pressure and/or other extensive parameters. The most characteristic levels of energy for substances are the ones determined by gas-crystal transition at zero pressure, in the ideal case. For monatomic substances it corresponds to the heat of atomization, for multi-atomic it can, possibly, be determined as the heat of atomization minus the energy of the molecules' formation. The heat of sublimation for many substances is close to the heat of condensation. The deep under-cooling of vapor is complicated or even improbable: for each particle almost enough latent heat of condensation exists for its emission when taking into account the width of levels. Hence, we can predict the range of radiation during the crystallization of a vapor phase. During the phenomena of melt crystallization the situation is more complicated. For transition to the radiating level, the heat of crystallization is not obviously enough; therefore, additional energy can be achieved by overcooling and/or when borrowed from the thermal energy of the melt. The additional energy, we assumed (Tatarchenko, 1979), can be equal to the activation of self-diffusion energy or to the energy of viscous flow. The following opportunities for the ranges of radiation exist: A. If radiation has one-photon character,
(Here uncertainties can be connected to the differentiation of bonds of formation of small clusters). E. A more complicated situation can not be a priori excluded: the aggregation of M particles and, additionally, q = 1, 2, 3, …m (m is the maximal coordination number) bonds with n-photon emission. The situation would mean the emission of (M + q/m) times the latent energy for one bond: ðM Þ
λn;m ≈
ð1Þ
Here the energy of emitted photon is ℏω1; NA is the Avogadro number; the latent energy of phase transition Λ is expressed in kJ/ mole, and the length of the radiation wave λ—in µm. B. The n-photon transition with equal frequencies: ℏωn = Λ = nNA
Or
λn = 120n = Λ :
ð2Þ
Here n is the number of formed bonds in the condensate, i.e. it can be less than or equal to the coordination number m: n = 1, 2, 3, …m. The singularities of the spectra of the condensate media can describe the number of bonds, i.e. their structure, at least for simple substances. 1 For monatomic substances the two-photon emission in the S0 state with unchanging symmetry of systems are most probable.
120n = ðM + q = mÞ Λ
ð5Þ
This expression can be applied to the appearance of certain bonds even at the stage of cluster formation. Thus, a character of the phase transition can be established on the basis of spectroscopy of the effect under investigation. Now, let us consider the mechanisms of snow and hail formation in the atmosphere. Hailstone formation occurs in two steps: first—the formation of water drops by condensation of water vapor; secondly—freezing of the water drops. Thus, there are two first order phase transitions. Snowflakes are formed by the direct deposition of water vapor, so there is one first order phase transition. Each of these three phase transitions (condensation–λ(C), freezing—λ(F), and deposition—λ(D)) can give the corresponding characteristic spectrum λ(C,M) ,λ(F,M) and λ(D,M) respectively. n n n The characteristic radiation wavelengths for one produced photon, and for each phase transition type of water with respect to relation (1), must be the following: ðC;1Þ
λ1
= 2:90μm;
ðF;1Þ
λ1
= 19:62μm;
ðD;1Þ
λ1
= 2:53μm
Similarly the characteristic radiation wavelengths for two produced photons, and for each phase transition type of water with respect to relation (2), have to be the following: ðC;1Þ
λ2 ℏω1 = Λ = NA ; that corresponds to λ1 = 120 = Λ;
ð4Þ
= 5:80μm;
ðF;1Þ
λ2
= 39:24μm;
ðD;1Þ
λ2
= 5:06μm:
For two photons produced, taking into account Doppler's broad(C,1) ening of the characteristic radiation, the following ranges for λ2 and (F,1) (C,1) λ2 were estimated by Mestvirishvili and Perelman (1977): λ2 = (F,1) (5.2–6.4) µm and λ2 = (34–42) µm. Thus, the increased intensities of radiation were found by (C,1) (F,1) Mestvirishvili et al (1977) in the ranges that include λ2 and λ2 . The experimental results of Nichols and Lamar (1968) correspond to (C,1) λ2 , taking into account a low pressure of vapor condensation. Nobody has ever explained, why IR radiation with λ ∼ (6.7–6.9) µm is effective for atmospheric water detection [see, for instance, Hasler (C,1) et al]. With respect to our model, it closely corresponds to the λ2 range of water phase transition characteristic radiation. The radiation peaks at ∼ 3.2 µm, 2.10 µm and 1.54 µm from Potter and Hoffman (1968) experiments as well as 1.05 µm and ∼0.9 µm from Ayad (1971) experiments, when taking into account the relation (4), can be attributed to the emission of two photon radiation during
V.A. Tatartchenko / Earth-Science Reviews 101 (2010) 24–28
condensation of water dimmers and higher molecular complexes: (C,2) (C,3) (C,4) (C,6) λ2 ∼ 3.2 µm, λ2 ∼ 2.10 µm, λ2 ∼ 1.54 µm, λ2 ∼ 1.05 µm, (C,7) λ2 ∼ 0.9 µm. It has to be mentioned that in experiments by Potter and Hoffman (1968), the condensed water forms a thin film on the glass surface. The water molecules have more adhesion to the glass surface than to each other, and as a result of this, the lower energetic level of phase transition is located deeper than the level in larger volumes of water. Superheated vapor on the cooled glass surface was also present in this experiment. Therefore, a complimentary reason could be vapor superheating and, as a result, raising of the upper energetic level. Both of these effects can increase the photon energy. The complementary bands in the spectrum of the water vapor discharge laser can be connected to the emission of four photon radiation during condensation of water and two-four photon (C,1) (F,1) radiation during freezing of water: λ4 ∼ 11.83 µm, λ2 ∼ 038.1– (F,1) (F,1) 39.7 µm, λ3 ∼ 57.8μm, λ4 ∼ 79μm. Thus, we presented here the data concerning water phase transitions and our interpretation of them. The feasibility of emissive phase transition in terms of the superradiation theory was considered by Sall' and Smirnov (2000). Their estimation shows that this transition can occur in an ensemble including more than 105 particles. As applied to water phase transition, this is on the order of a fog droplet or a hailstone's minimal dimensions. The problem of characteristic radiation yield has not been solved yet in the frame of the theories mentioned above. It is evident that the yield, first of all, depends on the transparency of both phases. But here the transparency problem is a very specific one. Indeed, using a laser analogy, our system contains the main level and the exited one. So, the system can work as an amplifier for the characteristic radiation and, in some conditions, to be transparent to it. Practically, homogeneity and geometry of the system under consideration are very important. This is the only explanation for the detection of the characteristic radiation of phase transitions for water and ice. Both these substances are nontransparent for recorded IR radiation. In experiments of Shibkov et al. (2002), a small part of the latent heat of water freezing was additionally emitted in the electromagnetic range. The theory of this phenomenon has been recently suggested by Perel'man et al. (2008).
3.
4.
5.
6.
7.
8.
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characteristic radiation exists, the system would work as a laser. For the 8% laser efficiency the energy of 2 kJ would be accumulated. A movement of the air inside the system with the speed 1 m/s would provide an impulse generator of 2 kW power and 1 Hz frequency. For comparison, a silicon solar cell of 1 m2 area provides approximately 100 W power. Hence, together with the energy of wind, falling water, and solar energy, fog and cloud formation could give us a forth source of ecologically pure energy. Formation of hail in storm clouds in the atmosphere has to be accompanied by intensive characteristic infrared radiation, which could be used to predict and warn of damaging hail storms. A program could be suggested to use this effect for the study of climate problems in the framework of the ARMP. The radiation under consideration must be included in all calculations of the heat balance in the atmosphere. Reemission of IR characteristic radiation in space, as a result of cloud formation in the upper atmospheric layers, is necessarily a very important source of the Earth's cooling. We could also use these radiation measurements to determine if there is water in the atmosphere of other planets, for instance in Mars' atmosphere. This radiation may explain Jupiter's red color and its infrared emission. It is well known that Jupiter emits more energy than it receives from the Sun. Circulation in Jupiter's atmosphere lifts the heated ammonium and water vapors, which are condensed and solidified in the upper part of the atmosphere. The IRCR of these processes seems to be the reason for the emission of Jupiter's infrared radiation and it displaces the planet's observable color in the red range. A similar process could be applied for the artificial cooling of the Earth: artificially creating upper atmospheric clouds by using the characteristic radiation and, as a result, causing heat emission into space.
Acknowledgements The author would like to thank Mme. E.V. Tatartchenko and Mr. J. Locher for fruitful discussions.
4. Conclusions There are a number of experimental and theoretical aspects still to be investigated. But even now, we can see the possibility of applying this phenomenon to climate problems. 1. According to the principles of QED, the presence of the described spontaneous transitions should lead to an opportunity to stimulate such transitions, for example crystallization, by irradiation of the substance, close to the temperature of crystallization, at a resonant frequency corresponding to the particular way of transition. Such opportunities, which until now have not been investigated experimentally, should uncover new effects. For instance, fog or ice clouds formation may occur as a result of atmosphere irradiation by characteristic radiation. At the same time, the primary laser beam will be amplified, and the energy of the water condensation or freezing in atmosphere can be accumulated. 2. Infrared lasers could be made on the basis of water vapor condensation or freezing in atmosphere. Let us imagine a system of two parallel mirrors (one of them is semitransparent) on an area of 1 m2 on the distance of 1 m each from other. Let us place this system in the atmosphere where the water vapor is saturating but is not condensed yet. Let us provoke condensing of the vapor (it is possible often to see a tail of water vapor behind a flying airplane). In this case about 10 g of water vapor will be condensed in our system. It means that 25 kJ of energy will be liberated. If the
References ARMP (Atmospheric Radiation Measurement Program), 2008. http://www.arm.gov/. Ayad, M., 1971. Electromagnetic radiation during ultrasonic cavitations. Infrared Physics 11, 249. Hasler, F., et al., 2003. NASA/GSFC and The GOES Project. (http://antwrp.gsfc.nasa.gov/ apod/ap020323.html). Mestvirishvili, A.N., Directovich, J.G., Grigoriev, S.I., Perel'man, M.E., 1977. Characteristic radiation due to the phase transitions latent energy. Physics Letters 60A, 143–144. Mestvirishvili, A.N., Perelman, M.E., 1977. Effect of conversion of a latent energy of first order phase transitions in a characteristic radiation. Proceeding of the Institute of Cybernetics 3, 338–357 (in Russian). Nichols, L.W., Lamar, J., 1968. Conversion of infrared images to visible in color. Applied Optics 7, 1757–1762. Perel'man, M.E., 1971. Phase transitions caused by the opening of new channels in electron–photon interactions. Physics Letters A 37, 411–412. Perel'man, M.E., Rubinshtein, G.M., Tatartchenko, V.A., 2008. Mechanisms of dendrites occurrence during crystallization: features of the ice crystals formation. Physics Letters A. doi:10.1016/j.physleta.2008.03.009. Perel'man, M.E., Tatartchenko, V.A., 2007. Phase transitions of the first kind as radiation Processes: arXiv: 0711.3570. Perel'man, M.E., Tatartchenko, V.A., 2008. Phase transitions of the first kind as radiation processes. Physics Letters A 372, 2480–2483. Potter, W.R., Hoffman, J.G., 1968. Phase transition luminescence in boiling water; evidence for clusters. Infrared Physics 8, 265–270. Sall', S.A., Smirnov, A.P., 2000. Phase-transition radiation and the growth of a new phase. Technical Physics 45, 849–853. Shibkov, A.A., et al., 2002. In situ monitoring of growth of ice from supercooled water by a new electromagnetic method. Journal of Crystal Growth 236, 434–440. Tatarchenko, V.A., 1979. Appearance of distinguishing features in emission spectra during crystallization of substances transparent in the IR region. Soviet Physics — Crystallography 24, 238–239.
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Tatarchenko, V.A., Umarov, L.M., 1980. Infrared radiation accompanying the crystallization of sapphire. Soviet Physics — Crystallography 25, 748–749. Tatarchenko, V.A., 1993. Shaped Crystal Growth. Kluwer, London. 288 pp. Tatartchenko, V.A., 2009. Some peculiarities of first order phase transitions. Reviews on Advanced Material Science 20 (#1), 58–69.
Tatartchenko, V.A., 2008. Characteristic IR radiation accompanying crystallization and window of transparency for it. Journal of Crystal Growth 310, 525–529. Umarov, L.M., Tatarchenko, V.A., 1984. Differential spectra of crystallization radiation of alkali-metal halides. Soviet Physics — Crystallography 29, 670–673.
Contents lists available at ScienceDirect
Earth-Science Reviews j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / e a r s c i r ev
Infrared characteristic radiation of water condensation and freezing in connection with atmospheric phenomena Vitali A. Tatartchenko Saint-Gobain Crystals, France
a r t i c l e
i n f o
Article history: Received 1 June 2008 Accepted 16 March 2010 Available online 28 March 2010 Keywords: First order phase transitions of water Condensation and crystallization Infrared radiation Atmospheric phenomena Formation of hail Jupiter Infrared laser
a b s t r a c t This paper considers the emission of infrared characteristic radiation during the first order phase transitions of water (condensation and crystallization). Experimental results are analyzed in terms of their correspondence to the theoretical models. These models are based on the assumption that the particle's (atom, molecule, or cluster) transition from the higher energetic level (vapor or liquid) to a lower one (liquid or crystal) produces an emission of one or more photons. The energy of these photons depends on the latent energy of the phase transition and the character of bonds formed by the particle in the new phase. Based on experimental data, the author proposes a model explaining the appearance of a window of transparency for the characteristic radiation in the substances when first order phase transitions take place. The effect under investigation must play a very important role in atmospheric phenomena: it is one of the sources of Earth's cooling; formation of hailstorm clouds in the atmosphere is accompanied by intensive characteristic infrared radiation that could be detected for process characterization and meteorological warnings. The effect can be used for atmospheric heat accumulation. Together with the energy of wind, falling water, and solar energy, fog and cloud formation could give us a forth source of ecologically pure energy. Searching for the presence of water in the atmospheres of other planets might also be possible using this technique. Furthermore, this radiation might explain the red color and infrared emission of Jupiter. © 2010 Elsevier B.V. All rights reserved.
Contents 1. Definition of the scope of discussion . . 2. IR radiation accompanying water phase 3. Experimental data discussion . . . . . 4. Conclusions . . . . . . . . . . . . . Acknowledgements . . . . . . . . . . . . References . . . . . . . . . . . . . . . .
. . . . . . transitions . . . . . . . . . . . . . . . . . . . . . . . . .
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1. Definition of the scope of discussion In our preceding papers (Tatarchenko, 1979; Tatarchenko and Umarov, 1980; Tatarchenko, 1993; Tatartchenko, 2008; Tatartchenko, 2009; Umarov and Tatarchenko, 1984) and in their references, evidence of infrared characteristic radiation (IRCR) emission during first order phase transitions was considered. For many substances (among them are water, alkali halides, sapphire, tellurium, germanium, sodium tiosulphate, and some metals), it seemed that the latent heat of melting was radiated directly by the melt crystallization into
E-mail address: [email protected]. 0012-8252/$ – see front matter © 2010 Elsevier B.V. All rights reserved. doi:10.1016/j.earscirev.2010.03.002
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the solid state, while the latent heat of vaporization was radiated directly by the vapor condensing into the liquid state. It is evident, therefore, that first order phase transitions, accompanied by the energy release, are sources of IRCR. Thus, our 46 year old assumption (Tatartchenko, 2008; Tatartchenko, 2009), that the particle's (atom, molecule or cluster) transition from a higher energetic level (vapor or melt) to a lower one (melt or crystal) produces emission of one or more photons, has been proven. In addition, there is definite evidence that photon energies depend on the latent energy of the phase transition and the character of chemical bonds in the new phase. In this paper, we discuss a specific aspect of this effect: the IRCR of the phase transitions of water in connection with atmospheric phenomena. We believe that specialists in different fields could
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25
significantly contribute to the solution of climate problems through further investigations of this phenomenon. Atmospheric radiation is one of the key subjects of atmospheric sciences, linking the fields of chemistry, aerosol, cloud physics, and thermodynamics to global climate and climate change. The Atmospheric Radiation Measurement Program (ARMP), created to resolve scientific uncertainties relating to global climate change, is focused on the crucial role of clouds and their influence on radiative feedback processes in the atmosphere [ARMP 2008 http://www.arm.gov/]. In the framework of ARMP, measurement of the intensity of IRCR accompanying water vapor condensation could provide significant information concerning cloud formation, as well as the energy balance in the atmosphere. Indeed, 40% of the solar energy reaching the Earth's surface is spent on water evaporation. The mechanism under consideration seems to play a very important role in the subsequent redistribution of this energy through condensation and crystallization in atmosphere, including its reemission into space. 2. IR radiation accompanying water phase transitions The data, concerning IR radiation appearance during water phase transitions, may be briefly stated as follows. Nichols and Lamar (1968) developed the idea of an infrared line scan camera. It scans an object simultaneously over three separate spectral ranges and produces an image of the object as a color photograph. The three spectral regions are 0.5–1.0 µm, 3.0–5.5 µm, and 8–14 µm. Each of the infrared spectral ranges is rendered in one of the primary colors—blue, green and red, respectively. As a result, the color of objects in a picture indicates their temperature and also their reflective and emissive properties. The numerous impressive pictures presented by the authors lead to the conclusion that they have indeed found sources of infrared radiation in the range of 8–14 µm in the atmosphere, which can be associated neither with temperature, nor with reflective radiation. These sources correspond to the bottom sides of cumulus clouds with a temperature of −5 °C and to the rising warm air saturated with water vapor. Unfortunately, we could not obtain high quality pictures to reproduce here. Potter and Hoffman (1968) describe experiments that were carried out in an apparatus comprising a vessel with boiling water, a cooled glass surface for vapor condensation, and a sensitive recording system for infrared radiation. An anomalous increase in infrared radiation intensity from the boundary between the glass surface and condensed vapor was observed. This intensity increased with increasing condensation rate. The integrated intensity was four times higher than Plank's radiation in the range of 1–4 µm. Two main emission bands were recorded in the vicinity of 2.10 µm and 1.54 µm (Fig. 1). The intensity of both bands exceeded the background radiation by a factor of ten. A third band with a wavelength of 3.2 µm, not mentioned by the authors, could possibly be detected on the curve of Fig. 1. When observing sonaro-luminescence, Ayad (1971) used a spectrometer with a thermocouple detector and a Lead Sulphide photometer. The peak of emission at wavelength 1.05 µm was detected. A second peak at 0.9 µm, not mentioned by the author, could possibly be recorded on the curve presented in the Ayad's paper. Mestvirishvili et al. (1977) recorded intense infrared radiation during water vapor condensation and water crystallization in a closed chamber. The temperature was lowered by adiabatic expansion. The radiation was observed through a Ge window in the chamber. Systems of filters and mirrors were used to pick out wide desirable IR ranges from the full spectrum. Radiation was detected by a bolometer. This technique allowed the authors to confirm that they had recorded the characteristic radiation for the condensation in the range of 4– 8 µm and for the crystallization in the range of 28–40 µm. The radiation intensity considerably exceeded the background Plank's intensity.
Fig. 1. From Potter and Hoffman (1968) paper. Relative intensity of the phase transition luminescence from water; Iw, intensity from the boiling water; Ibb, intensity from the black body.
In the case of the water vapor discharge laser, the main emission bands are ∼119 µm and 220 µm. On the other hand as it was mentioned by Mestvirishvili and Perelman (1977), few complementary bands have been recorded in its emission spectrum. Four of them, 11.83 µm, 38.1–39.7 µm, 57.8 µm, and 79 µm, which have not been identified, are of interest to us. Presently, a lot of infrared images of the Earth taken from Space exist. As a rule, 6.9–6.7 µm IR radiation of the Earth has been particularly useful for recording water vapor in the Earth's atmosphere. For instance, Hasler et al. (2003) confirm that the NASA orbiting GOES 8 satellite's multi-channel imager produces images of the upper troposphere at the infrared wavelength of 6.7 µm (Fig. 2). Bright regions correspond to high concentrations of water vapor over the oceans, while dark spots are relatively dry areas. 3. Experimental data discussion Evidence of the phenomenon under consideration does not follow from general phase transition concepts. As a rule, high-temperature luminescence has been rejected in favor of the phonon path of energy removal. We think it could be correct when applied to separate particles or to small clusters of a few particles. But in the case of a large number of particles, we believe IRCR has to occur. The phenomenon under consideration, it seems, occurs in the same way as nuclear fission reactions or laser radiation occurs. A critical mass depending on the system geometry is needed for all of these processes to take place. The feasibility of radiative phase transition in terms of quantum electrodynamics (QED) was treated for the first time by Perel'man (1971) and later in few papers including Perel'man and Tatartchenko (2007) and Perel'man and Tatartchenko (2008). Let us consider and refine the main points of two last papers applicable to water phase transition. We accept that when the particle (atom, molecule, or cluster) enters into a new phase, it radiates the latent heat of transition for this particle as one or several quanta which can be thermalized before they leave the substance. The presence of suitable levels of energy is necessary for radiation to occur. It has to be mentioned that the latent heat of condensation as well as the latent
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C. In the case of complex molecules, transitions with quanta of various frequencies is possible, e.g. for the two-photon case 0
ℏω1 = ℏω + ℏωq
λ0 ⋅λq 120 : = λ1 ≡ λ0 + λq Λ
Or
ð3Þ
More complicated combinations of frequencies can be similarly considered. D. Dimers and more complicated formations, clusters, can be examined as single particles and if the bond energy of atoms/ molecules in them is small enough, wavelengths of radiation for a cluster of M particles with n-photon emission will be of the type: ðMÞ
λn ≈120n = MΛ
Fig. 2. From Hasler et al. (2003) internet site. Earth image at the infrared wavelength of 6.7 μm, recording radiation emitted by water vapor in the upper troposphere. Bright regions correspond to high concentrations of water vapor, while dark spots are relatively dry areas.
heat of crystallization, are not constant; they both change with pressure and/or other extensive parameters. The most characteristic levels of energy for substances are the ones determined by gas-crystal transition at zero pressure, in the ideal case. For monatomic substances it corresponds to the heat of atomization, for multi-atomic it can, possibly, be determined as the heat of atomization minus the energy of the molecules' formation. The heat of sublimation for many substances is close to the heat of condensation. The deep under-cooling of vapor is complicated or even improbable: for each particle almost enough latent heat of condensation exists for its emission when taking into account the width of levels. Hence, we can predict the range of radiation during the crystallization of a vapor phase. During the phenomena of melt crystallization the situation is more complicated. For transition to the radiating level, the heat of crystallization is not obviously enough; therefore, additional energy can be achieved by overcooling and/or when borrowed from the thermal energy of the melt. The additional energy, we assumed (Tatarchenko, 1979), can be equal to the activation of self-diffusion energy or to the energy of viscous flow. The following opportunities for the ranges of radiation exist: A. If radiation has one-photon character,
(Here uncertainties can be connected to the differentiation of bonds of formation of small clusters). E. A more complicated situation can not be a priori excluded: the aggregation of M particles and, additionally, q = 1, 2, 3, …m (m is the maximal coordination number) bonds with n-photon emission. The situation would mean the emission of (M + q/m) times the latent energy for one bond: ðM Þ
λn;m ≈
ð1Þ
Here the energy of emitted photon is ℏω1; NA is the Avogadro number; the latent energy of phase transition Λ is expressed in kJ/ mole, and the length of the radiation wave λ—in µm. B. The n-photon transition with equal frequencies: ℏωn = Λ = nNA
Or
λn = 120n = Λ :
ð2Þ
Here n is the number of formed bonds in the condensate, i.e. it can be less than or equal to the coordination number m: n = 1, 2, 3, …m. The singularities of the spectra of the condensate media can describe the number of bonds, i.e. their structure, at least for simple substances. 1 For monatomic substances the two-photon emission in the S0 state with unchanging symmetry of systems are most probable.
120n = ðM + q = mÞ Λ
ð5Þ
This expression can be applied to the appearance of certain bonds even at the stage of cluster formation. Thus, a character of the phase transition can be established on the basis of spectroscopy of the effect under investigation. Now, let us consider the mechanisms of snow and hail formation in the atmosphere. Hailstone formation occurs in two steps: first—the formation of water drops by condensation of water vapor; secondly—freezing of the water drops. Thus, there are two first order phase transitions. Snowflakes are formed by the direct deposition of water vapor, so there is one first order phase transition. Each of these three phase transitions (condensation–λ(C), freezing—λ(F), and deposition—λ(D)) can give the corresponding characteristic spectrum λ(C,M) ,λ(F,M) and λ(D,M) respectively. n n n The characteristic radiation wavelengths for one produced photon, and for each phase transition type of water with respect to relation (1), must be the following: ðC;1Þ
λ1
= 2:90μm;
ðF;1Þ
λ1
= 19:62μm;
ðD;1Þ
λ1
= 2:53μm
Similarly the characteristic radiation wavelengths for two produced photons, and for each phase transition type of water with respect to relation (2), have to be the following: ðC;1Þ
λ2 ℏω1 = Λ = NA ; that corresponds to λ1 = 120 = Λ;
ð4Þ
= 5:80μm;
ðF;1Þ
λ2
= 39:24μm;
ðD;1Þ
λ2
= 5:06μm:
For two photons produced, taking into account Doppler's broad(C,1) ening of the characteristic radiation, the following ranges for λ2 and (F,1) (C,1) λ2 were estimated by Mestvirishvili and Perelman (1977): λ2 = (F,1) (5.2–6.4) µm and λ2 = (34–42) µm. Thus, the increased intensities of radiation were found by (C,1) (F,1) Mestvirishvili et al (1977) in the ranges that include λ2 and λ2 . The experimental results of Nichols and Lamar (1968) correspond to (C,1) λ2 , taking into account a low pressure of vapor condensation. Nobody has ever explained, why IR radiation with λ ∼ (6.7–6.9) µm is effective for atmospheric water detection [see, for instance, Hasler (C,1) et al]. With respect to our model, it closely corresponds to the λ2 range of water phase transition characteristic radiation. The radiation peaks at ∼ 3.2 µm, 2.10 µm and 1.54 µm from Potter and Hoffman (1968) experiments as well as 1.05 µm and ∼0.9 µm from Ayad (1971) experiments, when taking into account the relation (4), can be attributed to the emission of two photon radiation during
V.A. Tatartchenko / Earth-Science Reviews 101 (2010) 24–28
condensation of water dimmers and higher molecular complexes: (C,2) (C,3) (C,4) (C,6) λ2 ∼ 3.2 µm, λ2 ∼ 2.10 µm, λ2 ∼ 1.54 µm, λ2 ∼ 1.05 µm, (C,7) λ2 ∼ 0.9 µm. It has to be mentioned that in experiments by Potter and Hoffman (1968), the condensed water forms a thin film on the glass surface. The water molecules have more adhesion to the glass surface than to each other, and as a result of this, the lower energetic level of phase transition is located deeper than the level in larger volumes of water. Superheated vapor on the cooled glass surface was also present in this experiment. Therefore, a complimentary reason could be vapor superheating and, as a result, raising of the upper energetic level. Both of these effects can increase the photon energy. The complementary bands in the spectrum of the water vapor discharge laser can be connected to the emission of four photon radiation during condensation of water and two-four photon (C,1) (F,1) radiation during freezing of water: λ4 ∼ 11.83 µm, λ2 ∼ 038.1– (F,1) (F,1) 39.7 µm, λ3 ∼ 57.8μm, λ4 ∼ 79μm. Thus, we presented here the data concerning water phase transitions and our interpretation of them. The feasibility of emissive phase transition in terms of the superradiation theory was considered by Sall' and Smirnov (2000). Their estimation shows that this transition can occur in an ensemble including more than 105 particles. As applied to water phase transition, this is on the order of a fog droplet or a hailstone's minimal dimensions. The problem of characteristic radiation yield has not been solved yet in the frame of the theories mentioned above. It is evident that the yield, first of all, depends on the transparency of both phases. But here the transparency problem is a very specific one. Indeed, using a laser analogy, our system contains the main level and the exited one. So, the system can work as an amplifier for the characteristic radiation and, in some conditions, to be transparent to it. Practically, homogeneity and geometry of the system under consideration are very important. This is the only explanation for the detection of the characteristic radiation of phase transitions for water and ice. Both these substances are nontransparent for recorded IR radiation. In experiments of Shibkov et al. (2002), a small part of the latent heat of water freezing was additionally emitted in the electromagnetic range. The theory of this phenomenon has been recently suggested by Perel'man et al. (2008).
3.
4.
5.
6.
7.
8.
27
characteristic radiation exists, the system would work as a laser. For the 8% laser efficiency the energy of 2 kJ would be accumulated. A movement of the air inside the system with the speed 1 m/s would provide an impulse generator of 2 kW power and 1 Hz frequency. For comparison, a silicon solar cell of 1 m2 area provides approximately 100 W power. Hence, together with the energy of wind, falling water, and solar energy, fog and cloud formation could give us a forth source of ecologically pure energy. Formation of hail in storm clouds in the atmosphere has to be accompanied by intensive characteristic infrared radiation, which could be used to predict and warn of damaging hail storms. A program could be suggested to use this effect for the study of climate problems in the framework of the ARMP. The radiation under consideration must be included in all calculations of the heat balance in the atmosphere. Reemission of IR characteristic radiation in space, as a result of cloud formation in the upper atmospheric layers, is necessarily a very important source of the Earth's cooling. We could also use these radiation measurements to determine if there is water in the atmosphere of other planets, for instance in Mars' atmosphere. This radiation may explain Jupiter's red color and its infrared emission. It is well known that Jupiter emits more energy than it receives from the Sun. Circulation in Jupiter's atmosphere lifts the heated ammonium and water vapors, which are condensed and solidified in the upper part of the atmosphere. The IRCR of these processes seems to be the reason for the emission of Jupiter's infrared radiation and it displaces the planet's observable color in the red range. A similar process could be applied for the artificial cooling of the Earth: artificially creating upper atmospheric clouds by using the characteristic radiation and, as a result, causing heat emission into space.
Acknowledgements The author would like to thank Mme. E.V. Tatartchenko and Mr. J. Locher for fruitful discussions.
4. Conclusions There are a number of experimental and theoretical aspects still to be investigated. But even now, we can see the possibility of applying this phenomenon to climate problems. 1. According to the principles of QED, the presence of the described spontaneous transitions should lead to an opportunity to stimulate such transitions, for example crystallization, by irradiation of the substance, close to the temperature of crystallization, at a resonant frequency corresponding to the particular way of transition. Such opportunities, which until now have not been investigated experimentally, should uncover new effects. For instance, fog or ice clouds formation may occur as a result of atmosphere irradiation by characteristic radiation. At the same time, the primary laser beam will be amplified, and the energy of the water condensation or freezing in atmosphere can be accumulated. 2. Infrared lasers could be made on the basis of water vapor condensation or freezing in atmosphere. Let us imagine a system of two parallel mirrors (one of them is semitransparent) on an area of 1 m2 on the distance of 1 m each from other. Let us place this system in the atmosphere where the water vapor is saturating but is not condensed yet. Let us provoke condensing of the vapor (it is possible often to see a tail of water vapor behind a flying airplane). In this case about 10 g of water vapor will be condensed in our system. It means that 25 kJ of energy will be liberated. If the
References ARMP (Atmospheric Radiation Measurement Program), 2008. http://www.arm.gov/. Ayad, M., 1971. Electromagnetic radiation during ultrasonic cavitations. Infrared Physics 11, 249. Hasler, F., et al., 2003. NASA/GSFC and The GOES Project. (http://antwrp.gsfc.nasa.gov/ apod/ap020323.html). Mestvirishvili, A.N., Directovich, J.G., Grigoriev, S.I., Perel'man, M.E., 1977. Characteristic radiation due to the phase transitions latent energy. Physics Letters 60A, 143–144. Mestvirishvili, A.N., Perelman, M.E., 1977. Effect of conversion of a latent energy of first order phase transitions in a characteristic radiation. Proceeding of the Institute of Cybernetics 3, 338–357 (in Russian). Nichols, L.W., Lamar, J., 1968. Conversion of infrared images to visible in color. Applied Optics 7, 1757–1762. Perel'man, M.E., 1971. Phase transitions caused by the opening of new channels in electron–photon interactions. Physics Letters A 37, 411–412. Perel'man, M.E., Rubinshtein, G.M., Tatartchenko, V.A., 2008. Mechanisms of dendrites occurrence during crystallization: features of the ice crystals formation. Physics Letters A. doi:10.1016/j.physleta.2008.03.009. Perel'man, M.E., Tatartchenko, V.A., 2007. Phase transitions of the first kind as radiation Processes: arXiv: 0711.3570. Perel'man, M.E., Tatartchenko, V.A., 2008. Phase transitions of the first kind as radiation processes. Physics Letters A 372, 2480–2483. Potter, W.R., Hoffman, J.G., 1968. Phase transition luminescence in boiling water; evidence for clusters. Infrared Physics 8, 265–270. Sall', S.A., Smirnov, A.P., 2000. Phase-transition radiation and the growth of a new phase. Technical Physics 45, 849–853. Shibkov, A.A., et al., 2002. In situ monitoring of growth of ice from supercooled water by a new electromagnetic method. Journal of Crystal Growth 236, 434–440. Tatarchenko, V.A., 1979. Appearance of distinguishing features in emission spectra during crystallization of substances transparent in the IR region. Soviet Physics — Crystallography 24, 238–239.
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Tatarchenko, V.A., Umarov, L.M., 1980. Infrared radiation accompanying the crystallization of sapphire. Soviet Physics — Crystallography 25, 748–749. Tatarchenko, V.A., 1993. Shaped Crystal Growth. Kluwer, London. 288 pp. Tatartchenko, V.A., 2009. Some peculiarities of first order phase transitions. Reviews on Advanced Material Science 20 (#1), 58–69.
Tatartchenko, V.A., 2008. Characteristic IR radiation accompanying crystallization and window of transparency for it. Journal of Crystal Growth 310, 525–529. Umarov, L.M., Tatarchenko, V.A., 1984. Differential spectra of crystallization radiation of alkali-metal halides. Soviet Physics — Crystallography 29, 670–673.