Solar Energy Materials

and Solar Cells

ELSEVIER Solar Energy Materials and Solar Cells 38 (1995) 11-22

Thermodynamics of photochemical solar energy conversion

Alexis De Vos
Vakgroep voor elektronika en informatiesystemen, Universiteit Gent, Sint Pietersnieuwstraat 41, B·9000
Gent, Belgium

Abstract

Endoreversible thermodynamics is a subset of irreversible thermodynamics. Models are

simple as they only treat stationary situations, but nevertheless accurate as they can treat
situations far from equilibrium. We present both a chemical engine and a photovoltaic
engine. Brought together, these two engines can model a photochemical engine.

1. Introduction

Endoreversible thermodynamics form a subset of irreversible thermodynamics,

more specifically of finite-time thermodynamics [1,2]. Modelling and calculations
are easy because all irreversibilities are restricted to transports. No irreversibilities
are assumed to be related to conversions, mixings, etc. Thus the inner part of the
converter is reversible (EVOO meaning inner). Fig. 1a shows the endoreversible
thermochemical engine. We have three reservoirs at constant temperature T and
constant chemical potential JL. Reservoirs # 1 and # 2 are the external reservoirs
(source and sink, respectively); reservoir # 3 is the intermediate reservoir. Between
the reservoirs energy currents U and particle currents N are exchanged. We
assume no volume changes. Between reservoir # 1 and # 3 this happens by means
of an irreversible conductor; between # 3 and # 2 it happens by a reversible
engine. In both devices two axioms hold:
Nl = N3 = N2 (conservation of particles) ,
U 1 = U3 = U2 + W (conservation of energy),
where the N's denote particle currents, the U's denote energy currents and W
denotes the produced power. The fact that the inner engine is reversible means
that it satisfies a third axiom:
S3 = S2 (conservation of entropy),

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12 A. De Vos I Solar Energy Materials and Solar Cells 38 (J995) 11-22

w w

Fig.!. Endoreversible engines: (a) Thermochemical engine, (b) thermal engine, (c) chemical engine.

where the S's are the entropy currents (U - J.LN)/T associated with the currents
U and N.
The conservation of entropy, i.e.
U3 - J.L3 N 3 U2 - J.L2 N 2
T3 T2
together with the two other axioms, leads to
UI - J.L3 N I UI - W - J.L2NI
T3 T2
and therefore to a generalized Carnot formula:

W= (1 - T
T2) UI+T
3
( T2 J.L
3
3
- J.L 2 ) N l'

The Appendix gives an alternative form of this result.

For sake of completeness, we have to stress here that the equation NI = N3 = N2
only holds for the most simple chemical reaction. In a more realistic description,
we have to introduce stoichiometric coefficients.
The communication rate is assumed to be governed by transport equations of
the form
UI =/(TI,J.LI) -/(T3,J.L3) and NI =g(TI,J.LI) -g(T3,J.L3)'
where / and g are some known mathematical functions.

2. Thermal engines

Although the subject of thermal engines is not of direct concern here, we

present the thermal engine with linear conductor as an introductory example of
 A. De Vos / Solar Energy Materials and Solar Cells 38 (1995) 11-22 13

T3
0
1
1
1
1
W 1
__ 1____
W max
1
1
1 T3

t
0
(T3 )opt T1

\
Fig. 2. Characteristic of a thermal engine: (a) Refrigerator, (b) true heat engine, (c) heat pump.

how endoreversible thennodynamics lead to useful results in a simple way. In

purely thennal engines, there are only temperature differences and heat currents.
There are no potential differences (J.l.l = J.l.2 = J.l.3) and no particle currents (Nl =
N2 = N3 = 0). Fig. 1b shows an endoreversible thennal engine [3-5]: the heat
source at constant temperature Tl provides heat to a collector at temperature T3 ;
a reversible heat engine converts the heat current Ul into the work flow Wand
deposits the waste heat current U2 •
On the one hand, the rate of heat transport is governed by Tl and T3:

For given Tl and T 2 , the resulting rate Ul is thus function of the parameter T 3 •
Fig. 2 shows U l (T3 ). The detailed fonn of this curve depends on the particular
function f. An infonnative function f has the linear fonn
f(T) =aT,
where a contains, besides geometrical factors, a thennal conduction coefficient.
On the other hand, the efficiency of conversion of heat Ul into work W is
governed by T2 and T3 because of the Carnot rule W = (1 - T 2/T3)Ul • We thus
get
 14 A. De Vas / Solar Energy Materials and Solar Cells 38 (J995) 11-22

Fig. 3. Operational modes of a thermal engine: (a) Refrigerator, (b) true heat engine, (c) heat pump.

Fig. 2 also shows W(T3 ). We distinguish the following cases:

• for 0 < T3 < T2, we have U1 > 0 and W < 0: the engine works as a refrigerator;
• for T2 < T3 < T 1, we have U1 > 0 and W> 0: the engine is a true heat engine;
• for T3 > T 1, we have U1 < 0 and W < 0: the engine works as a heat pump.
Note that the border point T3 = TI between the last two operational modes
represents nothing else but the reversible operation, where energy conversion
happens with Carnot efficiency 1 - T2 /T1 , but infinitely slowly CUI = W = 0). On
Fig. 3, all three operational modes are shown, the thick arrows representing
positive energy fluxes.
The reader will easily verify that the condition dW/dT3 = 0 leads to an optimal
choice (T3)opt = /TIT 2 and to a maximum power production rate Wmax = a(.jT;
- {i;)2.

3. Chemical engines

In purely chemical engines, there are only potential differences. There are no
temperature differences (T1 = T2 = T3 = T) and no heat currents. Fig. Ic shows an
endoreversible chemical reactor [4-6]: the particle source at constant chemical
potential f-L1 provides particles to a collector at chemical potential f-L3; a reversible
fuel cell converts the particle current NI (reactant or fuel) into the work flow W
and deposits the waste particle current N2 (reaction product or exhaust).
On the one hand, the rate of particle transport is governed by f-LI and f-L3:
NI =g(f-LI) -g(f-L3)·

For given f-LI and f-L2' the resulting rate NI is thus function of the parameter f-L3.
Fig. 4 shows N I(f-L3). The detailed form of this curve depends on the particular
 A. De Vos / Solar Energy Materials and Solar Cells 38 (1995) 11-22 15

o I
I
I
I
WI
_..J ___ _
I
I
I

Fig. 4. Characteristic of a chemical engine: (a) Exhaust pump, (b) true chemical engine, (c) fuel pump.

function g. An important function g is derived from Fick's diffusion law and

:r ),
Nernst's law:

g ( }J.) = b exp (
where b contains, besides geometrical factors, a diffusion coefficient. This model is
applicable when the supply of fuel is limited by its transport towards the reversible
reaction chamber (i.e. transport from reservoir # 1 to reservoir # 3).
On the other hand, the conversion of energy into work W is governed by }J.3 and
}J.2 because of the 'Carnot' rule W = (}J.3 - }J.2)N1• We thus get e.g.

W= b(}J.3 - }J.2) [exp( :~) - exp ( : ; )]. (1)

Fig. 4 also shows the function W(}J.3). We distinguish again three cases:
• for}J.3 < }J.2' we have Nl > 0 and W < 0: the engine works as an exhaust pump;
• for }J.2 <}J.3 < }J.l' we have Nl > 0 and W> 0: the engine is a true fuel cell;
• for }J.3 > }J.l' we have Nl < 0 and W < 0: the engine works as a fuel pump.
On Fig. 5, the three operational modes are shown (the thick arrows representing
again positive currents). In both Figs. 5a and 5b, the reaction proceeds in the
forward or spontaneous direction, whereas in Fig. 5c, the reaction proceeds in the
reverse direction.
Again the border point }J.3 =}J.l is the reversible point. Again we have a
maximum-power point on the curve W(}J.3). Unfortunately, the condition dW/d}J.3
= 0 leads to a transcendental equation.
16 A. De Vos / Solar Energy Materials and Solar Cells 38 (J995) 11-22

Fig. 5. Operational modes of a chemical engine: (a) Exhaust pump, (b) true chemical engine, (c) fuel
pump.

For the more general case, with arbitrary stoichiometric coefficients, we have
W = J.L3N3 - J.L2N2. Calculations are somewhat cumbersome. Therefore, the reader
is referred to the appropriate Appendices of Refs. [4] and [6].

4. Photovoltaic engines
A photovoltaic engine is somewhat more complicated than a purely thennal
engine or a purely chemical engine, as both intensive variables T and J.L have to be
taken into account, such that it is a truly 'thennochemicaI' engine.
In a photovoltaic engine, the particles exchanged between reservoirs # 1 and #
3 are photons. From Bose-Einstein statistics with chemical potential [4,7], we can
derive the functions ! and g for radiative energy-and-particle exchange:
co E 3 dE 00 E 2 dE
!(T,J.L)=a{ (E-J.L) and g(T,J.L)=bjE (E-J.L) ,
• exp - - - 1 • exp - - - 1
kT kT
where k is the Boltzmann constant, E is the photon energy and Eg is the bandgap
of the radiative exchange. The proportionality coefficients a and b contain,
besides geometrical factors, the emissivities of both reservoirs.
A solar engine is an endoreversible thennochemical engine, where J.Ll =
(property of the Sun) and J.L2 = 0 (property of the Earth), but J.L3 is non-zero. It has
°
two degrees of freedom: the temperature T3 and the chemical potential J.L3 of the
solar collector.
When T3 equals T2 the solar engine is called a photovoltaic engine or solar cell
[4,5,8]. We have only one independent parameter anymore, i.e. J.L3' This chemical
potential is related to the cell's electrical voltage V simply by J.L3 = qV. From
Nt = g(T1,O) - g(T2 ,qV)
 A. De Vas / Solar Energy Materials and Solar Cells 38 (J995) 11-22 17

v
o

Fig. 6. Characteristic of a photovoltaic engine: (a) Photodiode, (b) true solar cell, (c) light-emitting
diode.

we deduce [7]

Nt(V) =b[{ exp - t~)kTt

-1
-{ exp
kTz
(:~~~)
-1
1·
Note that Nt is related to the cell's electrical current I simply by Nt = I/q. The
function I(V) is shown on Fig. 6. We distinguish three modes of operation of an
illuminated diode:
• for V < 0, we have I > 0 and W < 0: the diode works as a photodiode;
• for 0 < V < Voc ' we have I> 0 and W> 0: the diode works as a true solar cell;
• for V> Voc ' we have 1<0 and W < 0: the diode works as a light-emitting
diode,
where W = VI = JL3Nt or

W=bqv[f.:
exp -
r~d)
kTt
-1
-{ exp
(:~~~) 1
kTz
-1
(2)

and where Voc is the open-circuit voltage, i.e. the solution of the equation
Nt(V) = O. In contrast to Sections 2 and 3, the point of intersection with the
abscissa (i.e. V = Voc ) is not a reversible point, as reversibility in Fig. 1a requires
18 A. De Vos / Solar Energy Materials and Solar Cells 38 (J995) 11-22

Fig. 7. Operational modes of a photovoltaic engine: (a) Photodiode, (b) true solar cell, (c) light-emitting
diode.

simultaneous fulfilment of T3 = Tl and IL3 = ILl [4,9] and these conditions are not
respected here (neither at V = v"c nor at any other V), because of T3 = T 2 •
Finally, Fig. 7 shows the three operation modes.

5. Photochemical engines

A photochemical engine can be modelled as a chemical engine (Section 3),

powered by a photovoltaic engine (Section 4) [4,5]. As the sense of the arrows of
Figs. 5 and 7 have to match, we obtain only four different combinations (instead of
3 X 3 = 9, as one would expect at first thought). See Table 1 and Fig. 8. Note that
two out of the four modes can easily be given an appropriate name, but the other
two cannot easily be related to known phenomena or devices (as far as the author
is aware).
If the transport of power W happens reversibly, then not only the senses of the
W arrows have to match, but also their numeric values. This condition imposes a
relationship between the two variable parameters, i.e. IL3 of the chemical part and

Table 1
Operational modes of a photochemical engine
Figs. 5 and 7 -+ Fig. 8
5a+7b -+ 8a
5b+7a -+ 8b
5b+7c -+ 8c
5c+7b -+8d
 A. De Vas / Solar Energy Materials and Solar Cells 38 (1995) 11-22 19

Fig. 8. Operational modes of a photochemical engine: (a) Photodiode, (b) true solar cell, (c) chemolumi-
nescent cell, (d) true photochemical engine.

V of the photovoltaic part, such that we have only one degree of freedom instead
of two. The equation

(3)

where We is the power produced by the chemical part, given by expression (1), and
Wp is the power produced by the photovoltaic part, given by expression (2), is
visualised in Fig. 9. Note that the equation imposes minimum and maximum values
to both J.L3 and V. Finally, Fig. 10 is a graphical representation of Eq. (3). We have
a curved line, divided into four parts, representing the four operational modes.
The uppermost point on the closed curve has coordinates (V,J.L3) =
(Vopt ,(J.L3)max). It therefore not only represents the point of maximum power
transfer Uj, = - We' but also the point of maximum fuel production - N 1(J.L3). The
area within the closed loop represents operation of a photochemical engine where
the transport from one engine part to the other happens irreversibly, i.e. with
losses: w;, + Wp > O.

Fig. 9. Matching of a chemical engine to a photovoltaic engine.

20 A. De Vas / Solar Energy Materials and Solar Cells 38 (J995) 11-22

Fig. 10. Operational line of a photochemical engine: (a) Photodiode, (b) true solar cell, (c) chemolumi-
nescent cell, (d) true photochemical engine.

As an example, we can think of the (simplified) chemical reaction of photosyn-

thesis:
CH 2 0 + O 2 ~ CO 2 + H 2 0,
i.e. the oxidation of a carbohydrate molecule (e.g. glucose). The conductor g of the
chemical part of the photochemical engine consists of the stomatal pores of the
leaves, controlling the transport of the chemicals [4]. The photovoltaic part of the
photochemical engine is played by the chlorophyll. In normal conditions (i.e. in
day-time), the plant functions as a true photochemical engine (Fig. 8d). Therefore
the reverse reaction takes place, i.e. the synthesis of sugar.
Other photochemical engines can be modelled in the same way, e.g. solar-driven
hydrogen plants, where water electrolysis is powered by photovoltaic panels [10].
Watersplitting by direct photoelectrochemical systems is also possible [11-14].

1---" W

Fig. 11. Reversible thermochemical engine.

 A. De Vos / Solar Energy Materials and Solar Cells 38 (1995) 11-22 21

Other valuable chemicals can also be synthesized using sunlight directly [15,16].
Finally, toxic chemicals and pollutants can be destroyed photochemically [17,18].

6. Conclusion
In the present paper, we introduced successively different endoreversible en-
gines. First, as an introduction, we presented
• the endoreversible thermal engine.
Then, by analogy, we derived
• the endoreversible chemical engine and
• the endoreversible photovoltaic engine.
By putting together these two building blocks, we were able to construct finally
• the endoreversible photochemical engine.
In this way it was possible to model both qualitatively and quantitatively many
situations of irreversible thermodynamics. It was possible to link phenomena
described in the language of physicists (Section 2), chemists (Section 3) and
electrical engineers (Section 4).

7. Appendix: more about thermochemical engines

Sometimes it is useful to describe a chemical in terms of its specific enthalpy h
and specific entropy s, instead of its chemical potential JL. Therefore, the present
Appendix describes the lower part of Fig. la, i.e. the reversible thermochemical
engine, in terms of h's and s's.
For sake of completeness, we assume that the heat U3 is partly supplied by the
particle current N3 and partly not:
U3 = h3 N 3 + Q3'
where h3 is the specific enthalpy of the reactant and Q3 is some heat supplied in
addition to the energy h3N3 (e.g. by conduction). Analogously, we assume
U2 =h 2 N 2 +Q2'
where h2 is the specific enthalpy of the reaction product and Q 2 is some heat
drained away in addition to the energy h 2 N 2 • See Fig. 11, where again all
reservoirs are labelled by two intensive variables (i.e. temperature T and potential
JL) and all flows are labelled by two rates of extensive variable exchange (i.e. energy
U and particle number N).
We now apply
h j = JLj + 1';Sj'
where Sj is the specific entropy of the chemical. Restricting ourselves to the simple
stoichiometry N3 = N2 = N, the reader will easily verify that conservation of en-
ergy, i.e.
Q 3 +h3 N = Q 2 +h2N + W
leads to
W= Q 3 - Q2 + (h3 -h 2)N,
 22 A. De Vos / Solar Energy Materials and Solar Cells 38 (1995) 11-22

whereas conservation of entropy, i.e.

leads to

W= (1- ~: )Q3 + [(h3 - h 2) - T 2(S3 -s2)]N,

a generalized Camot formula. Finally, eliminating W from these two results, leads
us to a condensed form of the entropy conservation law:
Q3 Q2
- +S3 N = - +S2 N .
T3 T2

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