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Technology Scientific Ltd., 152 Ranch Estates, Dr. N.W., Calgary, Alberta, Canada T3G 1K4
Received 20 July 2006; received in revised form 12 September 2007; accepted 19 September 2007
Available online 12 October 2007
Abstract
The present paper contributes to the classic thermodynamic analysis of photosynthesis. Photosynthesis is a complex endothermic pro-
cess involving two kinds of matter; substance and radiation. This threefold study consists of: (1) an energy analysis (the energy conser-
vation equation is developed to estimate the energy effects of the process); (2) entropy analysis (the changes of entropy are used to
estimate the irreversibility of the component processes); and (3) exergy analysis (developed for thermodynamic evaluation of both kinds
of matter). A simplified mathematical diffusive model of photosynthesis (controlled by diffusion of gases) is used to analyze key aspects of
the problem. The corresponding terms of energy and exergy equations are compared and discussed. Photosynthesis is a highly irrevers-
ible process. In the calculation example the irreversibility loss is 97.4%. This increases slightly together with increasing temperatures of
leaf and environment. On the contrary, the energy equation does not show any loss due to irreversibility.
In the calculation example for the presented model, the exergy degree of perfection for photosynthesis is 2.61% and the energy degree
of perfection is 35.4%. The rate of sugar production is 3.21 · 109 kmol m2 s1. Heat transferred to the environment by radiation and
convection is respectively 6.4% and 65.3%. The exergies of the radiant and convective heat are 0.003% and zero, respectively. The impacts
on several output parameters (e.g. leaf temperature, sugar rate, degrees of perfection, etc.) were determined: the effect of varying input
conditions (e.g. environmental temperature and humidity, leaf absorptivity, intensity of solar radiation, coefficient of convective heat
transfer, and CO2 concentration). Some possibilities for further developing the exergy analysis are discussed.
2007 Elsevier Ltd. All rights reserved.
0038-092X/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.solener.2007.09.002
312 R. Petela / Solar Energy 82 (2008) 311–328
Nomenclature
Photosynthesis is very common as well as essential for rau and van der Merve (1968) and, with some more
life on the Earth. Detailed aspects of photosynthesis are details, by Jurevic and Zupanovic (2003). Jurevic and
discussed in many publications (Borror, 1960; Marchuk, Zupanovic introduce models for the mechanisms of photo-
1992; Vermaas, 1998; Campbell et al., 1999a,b; Purves synthesis. Based on statistical thermodynamics, Jørgensen
et al., 2003). Of course, the photosynthesis process occurs and Svirezhev (2004) developed thermodynamic theory of
according to the Second Law of Thermodynamics as is dis- ecological systems and evaluated some characteristic vari-
cussed for example by Brittin and Gamow (1961), Yourg- ables and data of mathematical biology.
R. Petela / Solar Energy 82 (2008) 311–328 313
The present paper is an approach to the photosynthesis Entropy can be used for process optimization by mini-
analysis based on the application of classic engineering mization of entropy generation. The overall or local irre-
thermodynamics and outlines the methodology of exergetic versible exergy loss can be calculated from the Guoy–
consideration of photosynthesis. The analysis of the subject Stodola law in which the respective entropy growth is
is complex due to involvement of diversified scientific disci- applied. However, the Second Law has limited application
plines (e.g. chemistry, thermodynamics with exergy analy- for micro systems containing denumerable number of inde-
sis, radiation, heat and mass transfer, etc.). Based on pendent particles. The smaller the number of particles, the
simplifying assumptions, a certain instantaneous model sit- less precisely the Second Law is fulfilled. For example for
uation is considered to obtain only preliminary energy, any micro biological system containing only a few compo-
entropy and exergy viewpoints. Because of the interdisci- nents the Second Law may be not fulfilled.
plinary character of the paper, short introductions to some The highest form of energy is mechanical energy, and
relevant disciplines are included. work is the most valuable method of energy transfer.
Therefore, exergy is defined as a maximum useful work
1.2. Significance of the thermodynamic analysis obtainable from the considered matter (substance or field
matter) in determined environmental conditions. Exergy
A critical understanding of thermodynamic analysis is alone, not the energy, expresses the real ability to do work.
essential. It can be applied to various processes of energy The full classic definition of exergy, as function of the states
conversion phenomena. Such analyses provide different of matter and environment, is given by Szargut in the book
(energy, entropy and exergy) views of the same process. of Szargut and Petela (1965b).
Typical analyses are based on the material conservation Exergy is the concept derived from simultaneous appli-
equations that are used for developing of energy balances, cation of the First and Second Laws of Thermodynamics.
calculation of entropies and, in the last decades, also for Irreversibility destroys the exergy. There is no exergy con-
providing supplementary exergy balances. servation law and exergy balance is completed with exergy
The First Law of Thermodynamics is developed to bet- loss; the greater the loss, the more irreversible the process.
ter understand any process, to facilitate design and control, Exergy balance allows the development of exergy analysis
to point at the needs for process improvement, and to according to the similar methodology of energy analysis.
enable eventual optimization. The degree of perfection of Exergy analysis applies to all applications mentioned for
energy utilization in the process, or its particular parts, energy analysis. Whereas thermodynamic probability is
allows one to compare the degree of perfection, and the expressed in units of entropy, exergy is expressed in energy
related process parameters, to those in other similar pro- units. Consequently, exergy data are more practical and
cesses. Comparison to the currently achievable values in realistic in comparison to the respective energy values.
the most efficient systems is especially important. As well, Thus, the exergy analysis provides a more realistic view
the priorities for the required optimization attempts for of process, sometimes dramatically different in comparison
the systems; or its components can be established. This to standard energy analyses.
can be done either according to their excessive energy con- The original monograph on exergy by Szargut and
sumptions or according to their particularly low degree of Petela (1965b, 1968), later developed also by Szargut
perfection. et al. (1988), is one of the pioneer approaches to exergy
However, the energy approach has some deficiencies. analysis theory. The monograph applies exergy analysis
Fundamentally, the energy concept is not sensitive to the to various processes, mostly to industrial processes. The
assumed direction of the process, e.g. energy analysis does analysis is based on classical thermodynamics and consid-
not object if heat is considered to be transferred spontane- erations are verified by numerous examples of applied engi-
ously in the direction of the increasing temperature. It also neering thermodynamics. The considerations in the present
does not distinguish the quality of the energy, e.g., 1 W of paper are based on the approach to exergy analysis devel-
heat equals 1 W of work or electricity. Energy analyses on oped in this monograph.
their own incorrectly interpret some processes, e.g., envi- Currently, there exist several different approaches to the
ronmental air, when isothermally compressed, maintains exergy analysis, Moran and Shapiro (1992), or Bejan
its energy (e.g. enthalpy) equal to zero, whereas the exergy (1997). They all are largely mutually consistent, equally
of the compressed air is larger than zero. valid and contribute to the better understanding of exergy
Entropy expresses the thermodynamic probability of analysis. Recently, the significance of exergy, used as a core
matter’s state. According to the Second Law of Thermody- thermodynamic variable for investigation of biological sys-
namics, the overall entropy growth in a process is required tems, was presented by Jørgensen and Svirezhev (2004) in
to always be positive. This requirement, applied even to an the case of ‘‘mathematical biology’’.
elemental step of any complex process, determines the only
possible direction in which the step can occur. Analysing 1.3. Some previous works and a scope of the present work
entropy allows for identification and location of the
sources of irreversibility contributing to the overall Energy analysis of green plants was previously dis-
unavoidable degradation of energy. cussed. For example, Spanner’s (1964) considerations of
314 R. Petela / Solar Energy 82 (2008) 311–328
the ‘‘economic’’ efficiency for photosynthesis led to the for- 2. Assumptions defining the simplified mathematical model of
mula (inadequate) for the exergy–energy ratio of radiation, photosynthesis
discussed later by Petela (2003).
However, the exergy analysis of photosynthesis process Fig. 1 presents a simplified scheme of the considered
became possible only after the theory of exergy of thermal photosynthesis. The system considered here is defined by
radiation was developed by Petela (1962). For the first the system boundary and contains a leaf surface layer in
time exergy analysis of plants was applied by Szargut which biomass is created at temperature T. Diffusion of
and Petela (1965a). In their calculations an exergy balance gaseous substances and convective heat transfer occurs
was carried out for 1 hectare area of forest over a 1 year through the gaseous boundary layer at the leaf surface.
period. It was assumed that: (1) the annual average exergy The boundary layer is not considered for radiation fluxes
of solar radiation arriving at the Earth’s surface is 10% of because it is assumed that air in this layer is transparent
the exergy of solar radiation arriving to the highest layer to radiation. The leaf surface absorbs part of the incident
of the Earth’s atmosphere; (2) the annual average water solar radiation and emits its own ‘leaf’ radiation of temper-
precipitation is 0.7 m/year; (3) the calorific value of wood ature T. The absorbed radiation is expended on the metab-
is 7635 kJ/kg; and (4) the wood mass increases by olism processes of the leaf and on maintaining the leaf
1350 kg. The exergy of generated wood was calculated temperature T above the environment temperature T0.
from the ratio (1.31) of chemical exergy to calorific value Liquid water, at temperature T, from the leaf body
determined by the authors. The exergy degree of perfec- enters the considered system. Only a relatively small
tion of the forest vegetation was relatively very small amount of this water is active in the assimilation of the
(0.033%) and the respective energy degree of perfection CO2, which diffuses into the leaf from the external environ-
was 1.4 times smaller. The growth of wood mass was ment. The large excess of water is transpired in the form of
related to the total radiation, not only to the PAR part vapour diffusing from the leaf to environment. Oxygen pro-
of the whole spectrum. duced during the photosynthesis also diffuses into the
Later, using the standard energy approach, photosyn- external environment. The water vapour and oxygen exit-
thesis was often analysed. However, exergy analyses have ing the boundary layer, as well as CO2 entering the bound-
seldom been applied. For example, Bisio and Bisio (1998) ary layer, have environment temperature T0 at the
discussed the approximate evaluation of the exergy effi- respective environment mole concentrations zH2 O;0 , zO2 ;0 ,
ciency and exergy losses whereas Reis and Miguel (2006) and zCO2;0 .
analysed the separated day and night processes. An The potential and kinetic components of exergy are
approach to photosynthesis, based on statistic thermody- neglected because the flow velocities of these substances
namics and exergy, was developed by Jørgensen and Svir- are very small and the leaf is insignificantly above the Earth
ezhev (2004). surface. Only the chemical and physical (sensible) compo-
In the present paper the exergy analysis of photosynthe- nents of the energy and exergy of the substances are consid-
sis is discussed in terms of the classic engineering thermo- ered. The physical component reflects the physical
dynamics. The analysis considers more details, involves parameters of the substance (temperature and pressure).
more process parameters and assumes that the diffusion The chemical component reflects the chemical composition
of gases controls the process. The primary version of this of the substance and is determined based on the devaluation
paper was submitted on September 1, 2005. reaction (Appendix B).
Ennvironment
of temperature T0 Total absorbed
solar radiation
H2 O
O2 vapor
CO2 Leaf
Visible Remaining radiation
part part Convection
Boundary heat
layer
H2 O Assumed system
boundary
liquid
The energy and entropy of radiation are calculated (x) The liquid water required for photosynthesis is avail-
according to Planck (1914). Values of radiation exergy are able in sufficient amount.
calculated from formulae derived by Petela (1962, 2003). (xi) In the considered conditions (as explained e.g. in
The complex photosynthesis mechanisms occurring in Fig. 7), the rate of sugar production is limited by
the leaf are not considered. Only the overall effects the effectiveness of diffusion of gases; not by the reac-
described by Eq. (1), and the matter fluxes observed around tion kinetics depending on temperature.
the leaf (Fig. 1), are analysed. The following conditions (xii) The generated sugar has only chemical exergy bch
have been also assumed: resulting from chemical reaction (1). Sugar exergy
gained as a result of ordering is neglected. The
(i) Considered is a conventional horizontal unitary ‘‘ordering’’ means the structure of the biomass in
(1 m2) surface of the leaf in a certain instant at the according to genetic plan, considered e.g. by Jørgen-
determined constant conditions. sen and Svirezhev (2004). Also neglected are any
(ii) To determine the actual energy arriving at the leaf other eventual component exergies, e.g. exergy due
surface, the solar radiation energy, of the spectrum to presence and necessity of chlorophyll as well as
measured at the highest layer of atmosphere, is mul- that which would reflect a mystery factor of life,
tiplied by a certain weakening factor c; the larger the etc. The including of any of these additional exergy
c, the smaller the weakening, (c 6 1). In the proposed components, some mentioned by Jørgensen and Svir-
simplified model the weakening factor is not studied, ezhev (2004), would also require the inclusion of the
nor is it concretely defined. Only certain possible val- respective component enthalpies in the energy conser-
ues of c are used in calculations. Some data, dis- vation equation from which the rate of the sugar pro-
cussed, e.g. by Iqbal (1983) or Muneer et al. (2004), duction is calculated. Without such adjustment the
could contribute to determination of the c factor. calculated rate would be so large that the exergy effi-
(iii) Cloudy situations are not analysed. ciency, taking into account the discussed exergy com-
(iv) The solar radiation arrives, directly from the sun in ponents, could be unfairly larger, possibly even larger
the zenith (solar radiation is perpendicular to the hor- than 100%.
izontal surface of the considered leaf), within the
solid angle determined by the diameter of the sun ‘‘Absorption’’ here means receiving radiant energy
and its distance from the Earth. Non-perpendicular which is not necessarily converted to heat. The terms
radiation could be expressed e.g. by appropriate ‘‘absorb’’ or ‘‘absorptivity’’ are interpreted respectively.
value of factor c. The term ‘‘radiation’’ means the ‘‘emitting process’’ or
(v) Sufficient chlorophyll necessary for the photosynthe- ‘‘emitted product’’; a photon gas.
sis process is available. Any change in the chlorophyll Further assumptions, in particular on some properties
concentration during photosynthesis, and the ther- of substances and radiation, are discussed in the next
modynamic effect of such change, are neglected. sections.
(vi) The surroundings of the considered leaf consists only The evaluation of the significance of each simplification
of the surfaces at temperature T0 and of absorptivity can be studied beyond the present paper. Some simplifica-
a0 = 1, (the sun surface area is neglected as being seen tions may not qualitatively affect the final conclusions,
within a relatively very small solid angle). although the quantitative results could be affected remark-
(vii) Mixtures of substances in the system are ideal; the ably. For example, the weakening factor c, could be deter-
components do not mutually interact. Therefore mix- mined through deep theoretical analysis, using all precise
ture properties are the respective sums of the compo- data on the diffusive loss of radiation energy with an
nents properties. For example, the biomass contained accounting of complex time-dependent geometrical config-
within the leaf structure is an ideal solution of solid uration of the leaf relative to the sun etc. Thus c can be
C6H12O6 and water. finally estimated at the specific value included in the range
(viii) The environment air contains only N2, O2, CO2 and of possible values in the presented model. In other words,
H2O. The dry environment air contains 79.07% N2, the problem lies mostly not in the model effectiveness but
20.9% O2, and 0.03% CO2, and the sum of mole frac- in determination of actual value of c to be applied in the
tions of these components is: zN2 ;0 þ zO2 ;0 þ zCO2 ;0 þ model. Obviously, the radiation arriving at the leaf could
zH2 O;0 ¼ 1, where zH2 O;0 is determined by the relative be accurately determined by measuring of the radiation
humidity u0 of the air and the saturation pressure ps0 spectrum directly at the leaf surface.
for the environment temperature T0: zH2 O;0 ¼ u0 ps0 .
(ix) The considered leaf has uniform temperature T; there 3. The substance properties
is no heat transfer within the considered surface layer.
According to the evaluation by Jørgensen and Svirez- 3.1. Energy of substance
hev (2004) there is a several degree difference D
between the leaf temperature and environment The considered substances in the system (Fig. 1) are gas-
temperature. eous CO2, O2, H2O (assumed to be ideal), liquid water and
316 R. Petela / Solar Energy 82 (2008) 311–328
the leaf substance (biomass). The enthalpies of the gases ation rn,SU = 979.71 kJ kmol1 K1 is given by Szargut
are zero because at the system boundary they have environ- and Petela (1965b). From Eq. (2) the calculated value of
ment temperature T0. However, for liquid H2O the water the absolute standard entropy is sn,SU = 2164.6 kJ
vapour is the reference phase. Therefore, the enthalpy of kmol1 K1. To calculate the absolute entropy sSU at any
liquid water is equal to the sum of negative value of the temperature T, the correction cSU · ln(T/Tn) is added.
latent heat of vaporization at temperature T0 and of the
temperature difference D = T T0 multiplied by the spe- 3.3. Exergy of substance
cific heat of water.
The generated biomass is assumed to be a mixture of As mentioned in Section 2, from all possible exergy com-
liquid water and sugar. The enthalpy of this mixture is cal- ponents only the physical bph and chemical bch exergy, are
culated as the sum of the component enthalpies. The taken into account to calculate the total exergy b =
enthalpy of sugar is the sum of the physical enthalpy and bch + bph of a substance. The exergy of each gas (CO2,
devaluation enthalpy. The physical enthalpy of sugar is cal- H2O and O2) is zero because in the considered case their
culated for the temperatures range from T0 to T at the con- states are in full equilibrium with environment.
stant specific heat, cSU = 430.227 kJ kmol1 K1, assumed, The total specific exergy bw of liquid water is approxi-
e.g. for an oak; Wisniowski’s (1979) data. mated (Appendix A) as a function of temperatures T and
The values of devaluation enthalpies dn for the standard T0, based on the Szargut and Petela’s (1965b) diagram.
parameters (pn = 101.325 kPa and temperature Tn = The exergy of the generated biomass is the sum of the
298.15 K) are tabulated, e.g., by Szargut et al. (1988). exergy of the components (liquid water and sugar). The
The variation of the devaluation enthalpy within the con- specific chemical exergy of sugar is determined based on
sidered temperatures range is negligible. Due to lack of the standard tabulated value bn,SU = 2,942,570 kJ kmol1,
data, the devaluation enthalpy d n;C6 H12 O6 d n;SU ¼ to which the correction for the difference of temperatures
2; 529; 590 kJ=ðkmol of sugarÞ is assumed to be similar to Tn and T0 is added (Appendix B):
that for a-D-galactose, predicting that the devaluation
Tn T0
enthalpy of the real substance generated in the leaf differs bch;SU ¼ bn;SU þ ðd n;SU bn;SU Þ ð3Þ
Tn
insignificantly. Such an assumption is supported by the fact
that the devaluation enthalpies tabulated for the substances The specific physical exergy of sugar is
of the same chemical formula (a-D-galactose and L-sor- T
bose), differ insignificantly. bph;SU ¼ cSU ðT T 0 Þ T 0 cSU ln ð4Þ
T0
3.2. Entropy of substance as explained in Appendix B.
5. Balances equations and liquid water in the produced biomass. The extracted
energy consists of the enthalpies of oxygen and water
5.1. Mass conservation equations vapour as well as convective heat and emission exchanged
by the leaf surface:
The mass fluxes, kmol/(m2 s), of CO2 and O2 are deter-
mined by the stoichiometric factors of Eq. (1): c½aV jV þ aL ðjS jV Þ þ nCO2 hCO2 þ nw hw
nCO2 ¼ 6nSU ; nO2 ¼ 6nSU , where nSU is the amount of pro- ¼ nSU hSU þ nwL hw þ nO2 hO2 þ nH2 O hH2 O þ qk þ eL ð14Þ
duced sugar (kmol) within period of 1 s and per 1 m2 of
irradiated leaf surface. where c is the radiation weakening factor and aV and aL are
The mass flux nw of water entering the leaf includes: (a) the absorptivities of the leaf within and beyond the PAR
water nwL within the generated biomass, (b) 6 · nSU of wavelength range, respectively.
water entering the chemical reaction (1), and (c) water According to assumption (vii), Section 2, the biomass is
nH2 O vaporized into environment. Thus, nw ¼ nwL þ an ideal solution of sugar and water. The total enthalpy of
6nSU þ nH2 O where nwL = nSU(1 zSU)/zSU and where zSU the biomass is the sum of the respective components;
is the mole fraction of sugar in the biomass composed of nSU · hSU + nwL · hw.
sugar and water. The heat (qk) transferred by convection from the leaf
As discussed by Jørgensen and Svirezhev (2004), an surface to the environment is qk = k(T T0), where k is
important factor in the determination of the effectiveness the heat transfer coefficient. Eq. (14) is used to calculate
of photosynthesis is the mole ratio r ¼ nH2 O =nCO2 of the the unknown rate nSU. The leaf temperature T is higher
water vapour and carbon dioxide rates. Water vapour dif- than the environment temperature T0 by the difference D:
fuses from the internal surface of the leaf, through the sto-
mata and intercellular space, towards the external surface T ¼ T0 þ D ð15Þ
of the leaf, and then diffuses through the boundary layer
to the atmosphere. The water rate, nH2 O , is proportional as discussed in Section 2; assumption (ix).
to the generalized coefficient DH2 O of diffusion and to the
difference ðzH2 O;L zH2 O;0 Þ, where zH2 O;L is the initial mole 5.3. Entropy equation
concentration of vapour at the inner surface and zH2 O;0 is
the final mole concentration in environment. Diffusion of The irreversibility of photosynthesis processes can be
carbon dioxide occurs in the opposite direction and is also evaluated using overall entropy growth P, which comprises
proportional to the generalized CO2 diffusion coefficient the entropy changes occurring as consequences of the pro-
DCO2 , and to the respective difference of mole concentra- cess. For example, the sun emits radiation regardless to the
tions zCO2 ;0 and zCO2 ;L . Therefore the rates ratio is: presence of the considered leaf, and the space is filled with
DH2 O zH2 OL zH2 O0 M H2 O this radiation (photon gas) with its respective entropy.
r¼ ð12Þ
DCO2 zCO2 0 zCO2 L M CO2 When the considered leaf becomes exposed, then a portion
of the incident solar radiation from space is absorbed by
where M H2 O and M CO2 are the molecular masses of H2O the leaf. Thus, the respective radiation entropy sS disap-
and CO2. The diffusion coefficients ratio was estimated pears and that needs to be taken into account. Other con-
by Jørgensen and Svirezhev (2004) as DH2 O =DCO2 1:32 sequences are the convective and radiative heat transfer
and according to Budyko (1977):zCO2 ;0 zCO2 L 0:1zCO2 0 . from the leaf to the environment of temperature T0. Added
It is also assumed that the concentration of water consequences are the appearing and disappearing entropies
vapour within the leaf corresponds to the saturation pres- of substances taking part in the photosynthesis chemical
sure ps,T at temperature T, zH2 OL ¼ ps;T =p0 . Thus Eq. (12) reactions.
can be written as Therefore, entropy growth P consists of the positive
p u0 ps0 (appearing) entropies of generated sugar (sSU), liquid water
r ¼ 5:4 sT ð13Þ
p0 zCO2 0 (swL) in the generated biomass, released water vapour
(sH2 O ), oxygen ðsO2 Þ, net emission (sL) of the leaf, and con-
The ratio r is determined by the diffusion processes which
vective heat (sq). The negative (disappearing) entropies cor-
control the rate of reaction (1), accordingly to assumption
respond to carbon dioxide ðsCO2 Þ, water (sw), and absorbed
(xi) in Section 2.
radiation (sS). Therefore:
5.2. Energy equation
P ¼ nSU sSU þ nwL sw þ nH2 O sH2 O þ nO2 sO2 þ sL þ sq
The energy conservation equation was formulated for nCO2 sCO2 nw sw c½aV sV þ aL ðsS sV Þ ð16Þ
the system shown schematically in Fig. 1. The energy deliv-
ered consists of absorbed solar radiation and the enthalpies where sq = qk/T0.
of carbon dioxide and liquid water. The energy increase of As with enthalpy, the total entropy of the biomass is the
the system is determined by the rates of the sugar substance sum of the respective components; nSU · sSU + nwL · sw.
R. Petela / Solar Energy 82 (2008) 311–328 319
where db is the total exergy loss due to all irreversible pro- Output
Convection heat 65.3 8.16 0
cesses occurring within the system. The exergy loss can be
Radiation of leaf surface 6.4 0.79 0.003
determined by the Gouy–Stodola law: Liquid water in biomass 7.1 0.41 0.023
Water vapour 0 280.50 0
db ¼ PT 0 ð18Þ
C2H12O6 35.4 1.113 2.608
Again as for enthalpy and entropy, the total exergy of bio- O2 0 0.670 0
Loss 0 0 97.366
mass is the sum of the respective components; Subtotal 100 291.643 100
nSU Æ bSU + nwL Æ bw.
Total 0 191.643 0
have the parameters equal to the environment parame- increase of r occurs in conjunction with the increase of
ters. The exergy of convective heat is zero because it is nH2 O from 7.74 · 106 to 7.82 · 106 kmol m2 s1 and
released to the environment. The exergy of the leaf radi- with the decrease of nCO2 from 1.93 · 108 to
ation (0.003%) is small due to relatively low temperature 1.46 · 108 kmol m2 s1. The increased amount of water
of the leaf. It is significantly smaller than the respective vaporized from the liquid to the vapour state causes a
energy (6.4%). The exergy of liquid water contained in decrease of the rate of sugar production, nSU, from
the produced biomass is 0.023%, (positive). Unlike the 3.21 · 109 to 2.43 · 109 kmol m2 s1. Consequently,
enthalpy and energy analyses, exergy analysis shows the the energy degree of perfection, ge, decreases from
irreversibility loss. In this case it is relatively very large 35.42% to 28.64%. The exergy degree of perfection, gb,
(97.366%). decreases from 2.61% to 1.97% due to the increased
Table 1 presents also the entropy terms of Eq. (16). The amount of water in the vapour state.
terms show the agreement with the second law of thermo- The results shown in the other columns can be analysed
dynamics and illustrate the role of the particular input or similarly.
output fluxes in overall entropy growth. Column 5 shows the effect of reducing the assumed tem-
perature difference D from 5 to 3 K. That change causes
6.2. Responsive trends to the varying input parameters increases of the diffusive fluxes for both CO2 and H2O, as
well as the sugar rate, and both degrees of perfection.
The model was also used for the computation of the Column 6 shows that a 3% drop of aV (from 0.88 to
results shown in Table 2. These illustrate the trends of 0.85) causes a reduction of the sugar rate nSU from
the output data in response to changes in some input 3.21 · 109 to 3.11 · 109 kmol s1 m2. Both the energy
parameters. The values in column 3 of Table 2 are consid- and exergy degrees of perfection decrease respectively from
ered as the reference values for studying the influence of the 35.42% to 34.57% and from 2.61% to 2.60%.
varying input parameters on the output data. Therefore, Column 7 shows that a 2% increase of aL (from 0.05 to
each of the next columns (4 to 11) corresponds to the case 0.07) causes a decrease in the sugar rate from 3.21 · 109 to
in which the input is changed only by the value shown in a 3.32 · 109 kmol s1 m2. The energy degree of perfection
particular column, whereas the other input parameters decreases from 35.42% to 35.32%, while the exergy degree
remain at the reference level. of perfection remains practically the same (2.61%).
Column 4 corresponds to a change in the environment Column 8 shows that for an increase of the weakening
temperature T0, which increases from 293 to 298 K. The factor c (e.g. by 5%, from 0.7 to 0.75), the sugar rate and
5 K T0 increase causes a pressure, u0 · ps0, increase from both degrees of perfection respond with appropriate
0.93 to 1.27 kPa. Note also that the 5 K increase in temper- increases.
ature T, from 298 to 303 K, causes the pressure, psT, to Column 9 shows that when the heat transfer coefficient,
increase from 3.17 to 4.25 kPa. Consequently, the pressure k, increases by a factor of 2 (from 0.003 to
difference, psT u0 · ps0, increases and thus the ratio r 0.006 kW m2 K1, e.g. due to wind), then the sugar rate
increases from 401 to 537 kmol H2O/kmol CO2. The and both degrees of perfection decrease.
Table 2
Responsive trends of output to change of some input parameters
Quantity Units Ref. value Mono-variant changes of input parameters and resulting outputs
1 2 3 4 5 6 7 8 9 10 11
Input
T0 K 293 298
D K 5 3
aV 0.88 0.85
aL 0.05 0.07
c 0.7 0.75
k W/(m2 K) 3 6
u0 % 0.4 0.9
zCO2 0.03 0.06
Output
u0 Æ ps0 kPa 0.93 1.27 0.93 0.93 0.93 0.93 0.93 2.10 0.93
ps T kPa 3.17 4.25 2.81 3.17 3.17 3.17 3.17 3.17 3.27
r 401 537 336 401 401 401 401 194 200
nCO2 108 kmol/(m2s) 1.93 1.46 2.33 1.87 1.99 2.07 1.85 3.88 3.76
nH2 O 106 kmol/(m2s) 7.74 7.82 7.82 7.48 7.98 8.32 7.40 7.53 7.54
nSU · 109 kmol/(m2s) 3.21 2.43 3.88 3.11 3.32 3.46 3.08 6.47 6.27
ge % 35.42 28.64 55.36 34.57 35.32 37.27 20.66 55.34 54.39
gb % 2.61 1.97 3.14 2.60 2.61 2.62 2.50 5.48 5.09
R. Petela / Solar Energy 82 (2008) 311–328 321
ηe and ηb %
significant increases in sugar rate and of both degrees of
40
perfection.
As shown in column 11, the 2-fold increase in the con-
centration of zCO2 causes a significant growth in sugar rate
20
nSU (from 3.21 · 109 to 6.27 · 109 kmol m2 s1). Both
energy and exergy degrees of perfection also grow signifi- ηb
cantly to 54.39% and 5.09%, respectively. The profiles of 0
the CO2 concentration in the boundary layers at the leaf 270 280 290 300 310 320
surface are discussed in Section 6.6. T0 K
6.3. Relation between the environment temperature, leaf that if on the right hand side (diffusive range) the rate
temperature and rate of sugar generation nSU decreases with increasing T0, then on the left hand side
from the optimum, the rate nSU also has to decrease (with
The photosynthesis model described here also allows for decreasing T0). The latter happens due to critical role of the
studies of various interrelationships. For example, based chemical reaction kinetics – chemical reaction rates
on the reference data listed in Section 6.1, Fig. 2 shows decrease with decreasing temperature and that is not con-
the leaf temperature T and the rate nSU of sugar production sidered in the present paper. Therefore the real curve nSU
as functions of the environment temperature T0. With in Fig. 2, instead of following the dashed line, should bend
increasing environment temperature, T0, the leaf tempera- down from the value for a certain optimal environment
ture, T, grows, whereas nSU decreases. Fig. 3 shows how temperature (T0,opt). That is shown subsequently as a thick
both the energy degree of perfection ge and the exergy dashed line in Fig. 7. The explanation of the dashed parts
degree of perfection gb for photosynthesis decreased with of the curves in Figs. 3–5, is the same.
the increasing environment temperature T0.
Note that the dashed parts of the curves in Fig. 2 have 6.4. The ratio of vaporized water and assimilated carbon
only a theoretical meaning. This is because it is supposed dioxide rates
that for the low values of T0, the rate nSU of sugar produc-
tion is not controlled by the diffusion of gases but by the Another example of the considered relations is the anal-
reaction kinetics. Such a supposition can be derived from ysis of the important photosynthesis parameter r. For the
the statement by Jørgensen and Svirezhev (2004) that the reference input data listed in Section 6.1, Fig. 4 shows
optimal temperature of photosynthesis is T 298 K. That how the rate nSU and degree of perfection gb increase with
corresponds to an environment temperature T0 lower by D, decreasing r. Fig. 5 shows that the greater the T0 and the
i.e. T0, opt 293 K. The statement of the optimum means smaller u0, the greater is the r.
12
1000
Kinetic Diffusive 10
range range
800
nSU.109 kmol SU/(m2 s)
kmol/(m s)
2
600
6
-11
nSU
nSU.10
400
T K
ηb %
4
T
200
ηb
2
T0,opt
nSU
0 0
270 280 290 300 310 320 0 200 400 600 800 1000 1200 1400
T0 K Ratio r
Fig. 2. Influence of T0 on leaf temperature T and rate nSU of sugar Fig. 4. Influence of ratio r on the sugar rate nSU and the exergy degree gb
production. of photosynthesis perfection.
322 R. Petela / Solar Energy 82 (2008) 311–328
ϕ0=0.65
perature multiplied by the respective entropy growth:
600
400 dbch ¼ T 0 fnSU sSU þ nO2 sO2 nCO2 sCO2 ðnw nH2 O
ϕ0=0.9
nwL Þsw lch c½aV sV þ aL ðsS sV Þg ð24Þ
200
6.6. Increased carbon dioxide concentration in the leaf because, by neglecting the radiation reflected from the leaf,
surroundings only the net utilized solar radiation is assumed as the input
to the photosynthesis process. If the chemical energy of
This effect is considered on the bases of the simplified sugar were be related to the total radiation arriving in
model of the layer zones in the vicinity of the leaf surface, the leaf surface, as proposed e.g. by Szargut and Petela
Fig. 6. Adjoining the leaf surface is the boundary layer, (1965a), the degrees of the photosynthesis perfection would
Fig. 1. Between the boundary layer and environment there become even smaller.
exists a zone of mildly blown gas (blow layer). The blown The definition of efficiency is a matter of discussion and
gas can be, for example, a cold waste combustion product agreement. For example, photosynthesis efficiency can be
arising from combustion at a very large excess-air ratio. defined simply by the ratio of the values for the generated
Thus, the concentration of CO2 in the combustion product sugar and the absorbed radiation. In such cases the exergy
is not significantly larger that the CO2 concentration in the efficiency gB is always larger than the energy efficiency gE;
environment. The profiles of CO2 mole fractions are shown (gB/gE > 1). This is due to the fact that the denominator
in Fig. 6 for the case with a blowing gas, zCO2 ;B , (solid line), in energy efficiency is larger than the denominator in exergy
and for the case without a blowing gas, zCO2 ;0 , (dashed line). efficiency, whereas the numerator in the energy efficiency is
The blown gas has temperature T0. The mole fractions smaller than the numerator in exergy efficiency; (generally,
zH2 O;B of the water vapour in the blown gas and in the envi- devaluation enthalpy of the organic substance is smaller
ronment are the same; zH2 O;B ¼ zH2 O;0 ¼ u0 ps =p0 . than its exergy). For example, neglecting the terms for
Due to differences in respective concentrations, diffusion liquid water and CO2 as well as non-PAR in Eqs. (19)
transportation of species occurs, O2 out of the surface (not and (20), the efficiencies ratio is given by gB/gE = (bSU/
shown in Fig. 6), H2O from the leaf to environment, and bV)/(hSU /jV). For the data assumed in Section 6.1, the ratio
CO2 in the opposite direction into the leaf surface. The gB/gE = (2.94 · 106/0.516)/(2. 53 · 106/0.545) = 1.22 at the
length of the diffusion path for H2O is not significantly values gB = 2.74% and gE = 2.23%.
changed by the presence of the blown gas zone. The slightly Unlike photosynthesis, the exergy/energy efficiencies
increased concentration of CO2 insignificantly decreases ratio for technical devices, such as those converting solar
the relatively large oxygen concentrations zO2 ;B in the blow radiation to heat, is smaller than unity, gB/ gE < 1. For
layer, zO2 ;B zO2 ;0 . Thus the presence of the blown gas zone example, for a solar cooker with cylindrical-parabolic pro-
practically does not change the diffusion flux of O2. The file, the energy efficiency is always larger than the exergy
diffusion rate nCO2 increases due to the increased CO2 con- efficiency. Thus the efficiencies ratio gB/gE, for example as
centration difference, and, contrary to the no-blow case, determined experimentally by Ozturk (2004) and theoreti-
the exergy of the CO2 rate entering the system boundary cally by Petela (2005), is within the approximate range
is different from zero. The presence of the blown gas zone from 0.03 to 0.16.
impacts formula (13) only by the increased CO2 mole frac- The degrees of perfection considered in this paper are
tion from zCO2 ;0 to zCO2 ;B , Fig. 6. The approximate quanti- determined for favourable conditions. However, signifi-
tative effects of the increased CO2 concentration in the cantly smaller degrees of perfection could be obtained for
leaf surroundings are shown in Table 2, column 11. a vegetation system considered globally during a finite time
period. In such a situation the conditions fluctuate beyond
6.7. Remarks on the photosynthesis degree of perfection favourable values. As mentioned earlier, Szargut and
Petela (1965a) obtained a small exergy degree of perfection
The considered degrees of perfection ge and gb, are (0.033%) from the approximate analysis of the forest veg-
found as relatively small. They present the net values etation studied for one year in realistic conditions.
Distance
T0
z Environment
CO2 0
z
H2O O
Blow CO2 B
Blow layer
z
H2O
CO2
Boundary layer
Mole fraction
or temperature Leaf surface
T
0
L
Temperature
H2O
z z CO profile
profile H2Oprofile
z
The efficiency values given by various authors are simi- favours the exposed surface by neglecting its imperfectness
larly small. However, direct comparison of the values is dif- during the absorption of heat Q. Thus, from these three
ficult because of differently assumed conditions. possibilities, relating the photosynthesis process effect to
the exergy bS of the sun’s radiation is the one best justified
7. Some other remarks in this analysis.
However, from the comparative viewpoint of different
It is worthwhile commenting on some possible misinter- processes, the best justified definition of the efficiency of
pretations of the entropy and exergy of radiation emitted photosynthesis seems to be Eq. (20).
by the sun’s surface. For example, some researchers, It is worth noting that the use of the exergy of heat at
instead of the solar radiation entropy sS, erroneously intro- the sun surface could be justified only in an unreal theoret-
duce the smaller value of entropy calculated as a heat ical situation where the exposed leaf surface would be
(exchanged between the sun and the leaf) divided by the entirely in direct contact with the sun’s surface and the heat
sun temperature (e.g. 6000 K). exchange would reversibly occur at a zero temperature
In technical calculations of heat exchange the sun sur- gradient.
face is assumed to be at the equilibrium state (the sun’s sur-
face receives energy from the sun interior and emits this 8. Conclusion
energy into the surrounding space). The state of the sun’s
surface is represented by its effective temperature and the This methodology for understanding the exergy of pho-
emitted radiation spectrum. tosynthesis outlines a preliminary study of the photosyn-
Any surface beyond the sun, exposed to radiation from thesis process based on the simultaneous analyses of
the sun can be also at a stable temperature resulting from energy, entropy and exergy. The study introduces the
the energy of radiation absorbed and emitted. Using the devaluation enthalpy (for the fair comparison of energy
temperatures of the sun and the exposed surface, the effect and exergy balances), the formulae for arbitrary radiation
called ‘‘radiation exchanged heat Q’’, can be calculated (convenient for the use of measurements of any actual radi-
from the first law of thermodynamics. This effect is real ation spectrum), and formulates the limiting diffusion
and the energy efficiency of any device driven by an range of the process. The study determines the effects of
exposed surface can be related to the exchanged heat. the main process input parameters and describes the model
However, when one examines the situation based on the of CO2 photosynthesis. Multi-factored aspects of the prob-
second law of thermodynamics, the degradation of the lem are presented based on original computation results.
exchanged heat Q can be better understood. Note, that However, the analyses developed here cannot be directly
the entropy of solar radiation incident on the leaf is larger compared with literature data since the latter are relatively
than the entropy of heat at the temperature of sun surface. sparse and based usually on incompatible assumptions.
The problem can be also illustrated with the simple exam- The interdisciplinary subject of photosynthesis is very
ple of radiation emission from any blackbody surface. In complex and involves many areas of knowledge including
those cases the energy e = acT4/4 and entropy of the black- thermodynamics, theory of exergy, transfer of radiation
body emission is s = acT3/3. In contrast, the entropy, serr, energy, heat convection, gas diffusion, chemistry, thermo-
determined erroneously, as the emission divided by temper- chemistry, photochemistry, as well as data dependent on
ature, would be: ser = e/T = acT3/4 5 s. time, day, month, season, weather conditions, geometrical
From an exergy view point, the leaf receives radiation configuration, etc. To obtain even a preliminary under-
exergy, smaller than the exergy of heat Q. Undisputedly, standing of the energy, entropy and exergy changes occur-
only the exergy of radiation should be used in the exergy ring during photosynthesis, only a certain model
balance of the leaf surface. instantaneous situation, determined with many simplifying
However, as already mentioned, efficiency can be assumptions, has been considered. These assumptions can
defined in different ways. For example, the exergy of the be gradually reduced in the future.
sugar produced can be related either to the exergy of heat In the diffusive model of photosynthesis introduced
at the sun surface, Q · (1 T0/TS), or to the exergy bS of here, the rate nSU of global reaction (1) is limited by diffus-
sun radiation, Eq. (10), or to the exergy of heat absorbed ing gases and is schematically presented in Fig. 7 by the dif-
on the leaf surface, Q Æ (1 T0/TL). The exergy efficiency fusion curve (solid part). The other part (dashed) of the
increases successively through the above three possibilities diffusion curve has no practical meaning. The intersection
due to the decreasing values of the denominators in the effi- of the diffusion and kinetics curves defines a certain opti-
ciency formulas: Q Æ (1 T0/TS) > bS > Q Æ (1 T0/TL). mal environment temperature T0,opt at which the rate is
An exergy efficiency which relates the process effect to the maximum, nSU,max. At low leaf temperatures, (T < T0,opt),
decrease of the sun’s exergy, Q Æ (1 T0/TS), is unfair the photosynthesis reaction is controlled by its kinetics
because the exposed surface obtains only the solar radia- and the rate nSU decreases with decreasing temperature
tion exergy and the leaf surface is independent of irrevers- T0, as shown in Fig. 7 (dashed thick curve), whereas the
ible emissions at the sun’s surface. Relating the process dashed thin part of this curve also has no practical mean-
effect to the exergy of heat absorbed, Q Æ (1 T0/TL), ing. The reaction kinetics can be considered in the future.
R. Petela / Solar Energy 82 (2008) 311–328 325
nSU
In the present paper some of the above effects, which are
already known, are confirmed and approximately esti-
mated together with the effects newly disclosed.
The computation example discloses a dramatic differ-
s
ence in the respective values of the terms of energy and
tic
di
ne
ffu exergy balances (Table 1). Although both energy and exer-
ki
s
io
n gy viewpoints are true, the exergy interpretation seems to
nSU, max be more practical.
The observations formulated here on the macro inter-
pretation of photosynthesis based on exergy could be con-
fronted with (not considered in the paper) descriptions of
the component’s mechanisms of photosynthesis at the
T0,opt
T0 micro level. As a result, some new ideas could be found
to improve the formulation of the exergy approach. As
Fig. 7. Schematic presentation of the optimum of the photosynthesis well, based on exergy, better interpretations of the micro
reaction.
mechanisms could be obtained. For example, the exergy
analysis could be applied separately to the light and dark
reactions, or different kinds of plants could be examined.
As a consequence of the many assumptions, the calcu- In the future, more detailed exergy investigations on fac-
lated quantitative responses to the varying photosynthesis tors such as temperature, light intensity, photochemistry,
input are of a limited certainty. However, improved cer- CO2 concentration, chlorophyll concentration/property
tainty can be expected for the direction trends found in data, and application of fertilizers supplied through air,
response to the varying input parameters. These trends water and soil, could be developed for both the diffusive
are shown in Table 4 by the algebraic signs of the partial and kinetic ranges of photosynthesis.
derivative oM/oN, where M and N are any output and
input variables, respectively. With growing N, M can grow Acknowledgements
(+), drop (), or can remain unchanged (0). For example if
u0 grows then r decreases (), nSU increases (+), nw The author thanks the journal’s Associate Editor, Dr.
decreases (), etc. S.A. Sheriff, and the anonymous reviewers for their diligent
Some parameters can be controlled (e.g. T0, k, u0, zCO2 ) comments which have been used in this paper. The author
and some cannot. For example the factor c (which depends thanks also Dr. A. Hardin of Hardin Associates Technol-
on the weather conditions, time of day or year), aV and aL ogy Management, Edmonton, for some technical verifica-
(which are the properties of the plant, and self-modeling tion and many editorial contributions.
D), cannot be controlled. Regarding controllable parame-
ters, the presented diffusion model (T0 > T0,opt) suggests Appendix A. Exergy of liquid water
striving for:
Exergy of liquid water bw, kJ/kmol, is the sum
• Rather low temperature (T0) of the leaf surroundings. bw = bph + bch of the physical part bph and chemical part
• Low heat transfer coefficient k, (e.g. avoid wind). bch, where bch = R Æ T0 Æ ln(1/u0). Using the Szargut and
• High humidity u0 to reduce diffusion of vapour, and Petela (1965b) diagrams the approximation formula for
• Surroundings with increased concentrations of CO2 to calculation of the physical exergy bph of liquid water is:
intensify its diffusion. bph = a + bt + ct2, where a ¼ 23:22 þ 2:718 t0 þ
0:0675 t20 , b ¼ 2:689 0:5787 t0 þ 0:00767 t20 , and c ¼
0:117 1:05 103 t0 þ 2:7 104 t20 7:5 106 t30 and
where t0 = T0-273.
Table 4
Acceptable accuracy (shown in Fig. A.1) is obtained
Algebraic sign of the partial derivative oM/oN
within the ranges of the water temperature t = 10 30C
Output variable M Input variable N
and environmental temperature t0 = 10 – 30 C. If t = t0,
T0 u0 D zCO2 ;0 c aV aL k then precisely bch = 0. Any negative values of a calculated
r + 0 0 0 0 bph result from imperfectness of the approximation and
nSU + + + + + should be rounded up to zero. Imperfectness is illustrated
nw + + + +
by, for example, the value of the most inconvenient dis-
nH20 + + + +
nCO2 + + + + + crepancy which occurs for the minimum of the curves.
nO2 + + + + + Instead of the required zero, the interpolation formula
ge + + + + gives 0.6 kJ/kmol. However, the interpolation formula,
gb + + + + + even with such imperfectness, is useful because it allows
db + + + +
for significant simplification of the computations.
326 R. Petela / Solar Energy 82 (2008) 311–328
100
should be used in thermodynamic analysis. It simulta-
80
t0=20 C neously includes the energy and exergy aspects.
60 The stoichiometric devaluation reaction for a substance
40 is a combination only of the considered substance and the
t0=10 C
20 various reference substances. A good example of a devalu-
0
ation process is reaction (1) in which, beside the considered
-20
substance (C6H12O6), only the reference substances appear,
0 10 20 30 40 50 CO2, H2O and O2.
tC The devaluation enthalpy, dn, is calculated from the
Fig. A.1. Approximated physical exergy of water.
energy conservation equation for the process in which sub-
strates are supplied, and products are extracted, all at stan-
dard temperature and pressure.
Appendix B. Outline and significance of the devaluation The physical exergy bph of a substance, at the state
reaction concept determined by enthalpy h and entropy s, is defined as
bph ¼ h h0 T 0 ðs s0 Þ ðB:1Þ
Based on this concept, as discussed for example by Szar-
gut et al. (1988), the following are calculated: enthalpy where h0 and s0 are the enthalpy and entropy of this sub-
devaluation of substance (appearing in energy conservation stance at environment parameters T0 and p0. Calculation
equation), standard entropy of devaluation reaction (in the of the chemical exergy bch of substance is more complex,
entropy considerations) and, consequently, chemical exer- depending on its composition and based on the devaluation
gy of substance (appearing in the exergy balance equation). reaction.
The main properties of substances are enthalpy and The calculated standard values of the devaluation
entropy. In chemical processes, contrary to physical pro- enthalpy, and chemical exergy, are tabulated by Szargut
cesses, substances change and only chemical elements and Petela (1965b) or Szargut et al. (1988). If environmen-
remain unchanged. Therefore, to calculate the chemical tal temperature differs from the standard temperature,
energy of the substances of concern, reference substances then, using the data on dn and bn, the formula for the chem-
have to be assumed. ical exergy of condensed substances (solid or liquid), is cor-
Methods for the determination of the chemical energy of rected as shown by Eq. (3) for sugar.
substances differ mainly by the definition of reference sub- If a substance has a temperature different from the sur-
stances. For example, in the enthalpy formation method, rounding environment, then a physical component of
the references substances are the elements at standard tem- energy or exergy has to be included as shown by Eq. (4)
perature and pressure. In the devaluation reaction method for the exergy of sugar.
the number of reference substances is the same, however Note as well that based on the devaluation reaction, the
they are not the exclusively elements but the devaluated sub- so-called standard entropy rn of the devaluation reaction
stances (compounds or elements most commonly appearing can be determined. For example, for the photosynthesis
in the environment). For example, the reference substance of reaction, according to Eq. (1), the standard entropy of
C is gaseous CO2, for H2 it is gaseous H2O, and for O it is just the devaluation reaction, rn,SU, is
O2. In any particular case, when a substance is composed
rn;SU ¼ 6ðsH2 O þ sCO2 Þn ðsO2 Þn sn;SU ðB:2Þ
only of C,O,H,N, and S, then the devaluation enthalpy of
the substance is equal to its calorific value. where sH2 O ; sCO2 and sO2 are the absolute standard entropies
Contrary to the devaluation enthalpy, values determined of the respective gases. The stoichiometric factor of 6 re-
for the enthalpy of formation are not practical. For exam- sults from Eq. (1).
ple, the enthalpy of formation for C is zero and the
enthalpy of formation of CO2 is significantly different that Appendix C. Outline of derivation of some radiation
zero (394 MJ/kmol). However, the devaluation formulae
enthalpy of C is equal to the calorific value 394 MJ/kmol,
whereas the calorific value of CO2 is zero (as it is the refer- The main properties of radiation are radiosity j, its
ence substance for C). entropy s, and exergy b, which is of course based on j
The reference substances for devaluation enthalpy and and s. Radiation from an arbitrary source has an irregular
chemical exergy are the same. Also, the reference tempera- spectrum that is not expressible by something like an ideal
ture and pressure are the same. Thus, only the devaluation blackbody or a gray model. According to Planck, to deter-
enthalpy method, contrary to the formation enthalpy mine the arbitrary radiation energy (e.g. radiosity j), the
R. Petela / Solar Energy 82 (2008) 311–328 327
Z Z
smallest and the greatest component intensity values Km
cos h sin h dh du ¼ 2:16 105 p ðC:8Þ
and K 0m for monochromatic polarized radiation (depending h u
on oscillation frequency), or respectively Kk and K 0k
and, using Kk, formula (C.6) becomes:
(depending on wavelengths), are used: Z k¼1
Z Z 5
jS ¼ 4:329 10 p K k dk ðC:9Þ
j ¼ ðK m þ K 0m Þdm ¼ ðK k þ K 0k Þdk ðC:1Þ k¼0
m k
However, the integral in Eq. (C.9) can be analytically
For an unpolarized radiation K m ¼ K 0m and Kk ¼ K 0k , thus solved only for a blackbody spectrum. Thus for any arbi-
Z Z
trary spectrum a numerical solution is applied as show in
j ¼ 2 K m dm ¼ 2 K k dk ðC:2Þ Eq. (5).
m k
By analogy, using Lk from formulae (C.7) and (C.8), the
The radiosity entropy s can be expressed analogically, radiosity entropy is:
Z Z
Z k¼1
s ¼ 2 Lm dm ¼ 2 Lk dk ðC:3Þ
m k sS ¼ 4:329 105 p Lk dk ðC:10Þ
k¼0
where according to Planck, the respective entropy Lm and
and numerical solution applied to Eq. (C.10) leads to Eq.
Lk of the monochromatic energy components are
(7).
km2 The exergy, bS, of the considered solar radiation inci-
Lm ¼ ½ð1 þ X Þ lnð1 þ X Þ X ln X ðC:4Þ
c2 dent on the leaf surface can be derived with the one of Pete-
where X c2 Km/(m3h), or: la’s methods. For example, according to Petela (1974), the
definition of physical exergy for a substance, Eq. (B.1), can
ck be interpreted for radiation as follows:
Lk ¼ ½ð1 þ Y Þ lnð1 þ Y Þ Y ln Y ðC:5Þ
k2 bS ¼ jS j0 T 0 ðsS s0 Þ ðC:11Þ
where Y k5 Kk/(c2h).
It is emphasized that Kk, or Km, for any arbitrary spec- where j0 and s0 are respectively the radiosity and its entropy
trum, are measured values, whereas the calculation formu- for radiation at an environmental temperature T0. Assum-
lae for these magnitudes are available only for ideal ing the environment to be a blackbody surface, the radios-
blackbody spectrum. ity j0 of radiation uniformly propagating from that surface,
The configuration for incident radiation exchange within the solid angle determined by coordinates h and u,
between the leaf and sun can be described by the angle can be interpreted as follows:
Z Z
coordinates h and u (azimuth and declension) of the direc- Cb 4
j0 ¼ T0 cos h dh du ðC:12Þ
tions included within the solid angle in which the sun is p h u
seen from a point at the considered leaf surface. Thus,
and by analogy:
the solar radiosity, jS, arriving in the leaf surface can be Z Z
assumed as 4 Cb 3
ZZZ s0 ¼ T0 cos h sin h du ðC:13Þ
3p h u
jS ¼ 2 K m cos h sin h dh du dm
m h u Using (C.6), (C.7), (C.12), (C.13) and (C.8) in (C.11), Eq.
ZZZ
(10) is obtained.
¼2 K k cos h sin u dh du dk ðC:6Þ
k h u
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