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Thermodynamic Optimization of Energy Transfer in (Bio) Chemical Reaction Systems
Thermodynamic Optimization of Energy Transfer in (Bio) Chemical Reaction Systems
Thermodynamic Optimization of Energy Transfer in (Bio) Chemical Reaction Systems
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Abstract
The engineering science literature on energy-transfer processes (heat engines, heat pumps, etc.) for the production of mechanical energy,
electricity, cold or heat has produced some remarkable results on maximum power and e3ciency optimization. We have wondered in how
far these results can be extended to include chemical reaction systems to describe living and possibly future-industrial energy-transfer
systems. With elements of non-linear irreversible thermodynamics and chemical kinetics, we have arrived at some interesting results on
optimizing the performance of chemical energy transfer. We discuss thermodynamic e3ciency, energy-transfer rate, entropy-generation
rate, and optimum-performance characteristics of (bio)chemical energy transfer.
? 2003 Elsevier Science Ltd. All rights reserved.
0009-2509/03/$ - see front matter ? 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0009-2509(03)00026-5
2002 S. Lems et al. / Chemical Engineering Science 58 (2003) 2001 2009
is reduced, more of the heat in the :uid stream will simply 3. Model for chemical energy transfer
leave the heat exchanger and :ow irreversibility to TL as ex-
ternal heat loss Q ex , which also leads to a smaller W . It was A chemical reaction system is considered as given in
found that at maximum power output the e3ciency
of the Fig. 2. Chemical energy is transferred at 298:15 K in a cou-
whole power plant operating between temperatures TH and pled chemical reaction in which the thermodynamically fa-
TL is vorable (downhill) reaction of compound C to D (reaction
1=2 CD) drives the thermo-dynamically unfavorable (uphill) re-
TL
Fig. 3. Graphical presentation of the energy barrier (Eyring, 1935; Eyring Fig. 4. Non-linear relation between the rate and a3nity of a chemical
& Eyring 1963) between the reactants and products of a chemical reaction. reaction.
biochemical reactions take place. The work potential of a rate is related to the reaction a3nity (A) as
chemical reaction is then determined by the reaction a3nity
v
(A), as deJned by DeDonder (1927). = eA=RT : (6)
The a3nity (A) of a chemical reaction expresses the de- v
gree of thermodynamic non-equilibrium between its prod- Combining Eqs. (6) with (5) yields the force:ow relation,
ucts and its reactants, and hence it is determined by the describing the net reaction rate as a function of the reaction
chemical potentials (i ) and stoichiometric coe3cients (i ) a3nity:
of the compounds participating in the reaction. In essence,
v = v (1 eA=RT ):
the a3nity is simply the negative value of the Gibbs energy (7)
change (Mr G) of the reaction:
The relation is clearly non-linear, as is given graphically in
A = Mr G = i i : (4) Fig. 4. The Jgure shows a diminishing marginal return on
i reaction rate at increasing reaction a3nity, which means that
a high reaction a3nity is less e3cient in making the reaction
At A 0 the products of the chemical reaction are at lower proceed spontaneously than a low a3nity. The non-linear
energy level than the reactants. The reaction then proceeds relation is in contrast to the often-used linear relation, which
forward until it reaches thermodynamic equilibrium, at only applies at conditions very close to equilibrium. This can
which A = 0. At equilibrium there is no longer a driving be directly obtained from the non-linear relation, because
force to make the reaction proceed in a uniform direction, only at very small reaction a3nity (A) does Eq. (7) reduce
and the reaction therefore has no more potential to perform to
work.
A
The second step in the mathematical description of the
lim v = v : (8)
model is determining the rate of a chemical reaction as a A0 RT
function of its a3nity. By considering the chemical reactions A linear force:ow relation in e.g. heat transfer can ap-
as elementary reaction steps, the transition state or activated ply quite well over large temperature diDerences, but for
complex theory applies, and, as follows from the formula- chemical reaction this near-linear region is particularly
tion of reaction rates by Eyring (1935); Eyring and Eyring small. Therefore, our model considers the reaction rates
(1963) the overall reaction rate v is then the net result of the vcoupled ; vCD , and vYX to be related to their forward reac-
forward reaction rate and the backward reaction rate:
tion rates v CD ; v YX , and v coupled , and to their a3nities
ACD ; AYX , and Acoupled , respectively, as given by Eq. (7).
v= vv: (5)
The value of v coupled is Jxed at 1 mol=s and the values
of v CD and v YX are determined relative to this value using
Fig. 3 illustrates the idea of the transition state theory and
the following method. The forward reaction rate v of each
shows that a positive reaction a3nity (A) leads to a higher
of the three chemical reactions is related to its activation
eDective energy barrier (MG act + A) for the backward re-
energy MG act as
action, while the energy barrier for the forward reaction re-
mains unchanged. As a result, the rate of the forward reac- v =k0 eMG
act
=RT
: (9)
tion exceeds the rate of the backward reaction, causing the
net reaction to proceed forward. As shown by De Donder Assuming for simplicity that k0 is the same for the dif-
(1927), the ratio between forward and backward reaction ferent reactions, the ratio of forward reaction rates of two
2004 S. Lems et al. / Chemical Engineering Science 58 (2003) 2001 2009
chemical reactions can be related to their diDerence in acti- e3ciency, and minimum entropy generation, respectively.
vation energy. These will be described separately in the next three sections.
Considering also that v CD and v YX are equal in value,
we can state
v coupled
v coupled
act act
MGleak MGcoupled 4. Maximum work output
= =e RT : (10)
v CD v YX
In analog to the optimization of heat-driven power plants,
act
In which MGleak is the activation energy of both leak reac- we can optimize the chemical system by adjusting the a3n-
tions CD and YX. ity of the coupled reaction (Acoupled ). The amount of work
We will refer to the exponential factor in Eq. (10) as delivered by the chemical system per unit of time is the
kinetic parameter : product of the reaction a3nity AYX and the eDective rate at
act
MGleak act
MGcoupled which compound Y is generated:
= : (11)
RT W out = (vcoupled vYX )AYX : (13)
The factor expresses the extent to which the coupled chem-
ical reaction is kinetically favored over the leak reaction. In Eq. (13), both the reaction rates and the a3nity are func-
At 0 the activation barrier of the leak reaction exceeds tions of Acoupled . The work output rate is therefore also a
the activation barrier of the coupled reaction, and hence the function of Acoupled , and this function is presented graph-
value of v coupled exceeds that of v leak ; At = 0 the cou- ically in Fig. 5. The Jgure shows two extreme situations
pled reaction and the leak reaction are equally favored, and at which no work output rate is obtained. At one extreme,
at 0 the value of v leak exceeds that of v coupled . Acoupled = 0 and chemical energy is transferred without loss
When assuming the diDerence in activation energies to be from reaction CD to reaction XY in the coupled reaction, but
mainly the result of catalysis of the coupled reaction, data the transfer occurs at zero velocity, i.e. at vcoupled = 0. The
on catalysis of chemical reactions allow the forward reac- work output rate is then zero or can even be negative since
tion rates of leak reactions CD and YX to be determined via chemical energy is continuously being dissipated in leak
Eq. (10). In this case can be considered a catalysis param- reaction YX. In the other extreme situation Acoupled = ACD
eter, expressing the extent to which the coupled reaction is and, although vcoupled is then maximal, all chemical energy
catalyzed over the leak reactions. is dissipated in the coupled reaction and none is transferred.
Finally, the a3nities of the three diDerent chemical reac- Again, no output of work is achieved.
tions to be related to each other as Between these extremes at 0 Acoupled ACD , chemical
energy is transferred with some loss but at a non-zero ve-
ACD = AYX + Acoupled : (12) locity. A maximum in the work output rate is achieved at a
Eq. (12) expresses the fact that the total available a3nity value of Acoupled where there is a balance between dissipation
ACD must pay for two diDerent eDects in the chemical en- and transfer of chemical energy. This result is analogous to
ergy transfer. First, reaction a3nity ACD must drive the ther- the results of Bejan (1996) for heat-driven power plants.
modynamically unfavorable reaction YX requiring a3nity To investigate the location of the optimum work output
AYX , and secondly it must make the coupled reaction oc- rate, we Jrst consider an ideal situation. In this situation,
cur spontaneously, which requires some positive value of leak reaction YX is absent, and the coupled reaction occurs
coupled-reaction a3nity Acoupled . so close to equilibrium, i.e. Acoupled is so small, that a linear
The value of reaction a3nity ACD used in the model relation between reaction rate and reaction a3nity applies.
is important, because it provides the room for non-linear
behavior in the chemical reactions. This value is Jxed at
50 kJ=mol, which resembles the situation in actual biochem-
ical energy-transfer reactions. The hydrolysis reaction of
one of the major energy carriers in cell metabolism, named
adenosine tri-phosphate or simply ATP, was calculated to
have an a3nity ranging from 48 to 55 kJ=mol (Lems, 2001)
at diDerent intracellular conditions. The a3nity of ATP hy-
drolysis is maintained by many biochemical reactions, and
it is therefore quite constant. Likewise, the value of a3nity
ACD is taken constant in the model.
The performance of the model is optimized by varying the
a3nity of the coupled reaction Acoupled , which is a measure
for the driving force for chemical energy transfer. Focus
will be on three optimum points in the operation of the Fig. 5. Output of chemical free energy as a function of the coupled-reaction
model: maximum work output, maximum thermodynamic a3nity at diDerent values of .
S. Lems et al. / Chemical Engineering Science 58 (2003) 2001 2009 2005
= = : (18)
W in (vCD + vcoupled )ACD
As given in Eq. (18), the work input is not only the chem-
ical energy required to drive the coupled reaction, but it Fig. 7. E3ciency of chemical energy transfer as a function of the
coupled-reaction a3nity at diDerent values of .
also includes the chemical energy dissipated in leak reac-
tion CD.
The e3ciency is a function of Acoupled , and, as shown in
Fig 7, this function and the location of its optimum depends
on the values of . In an ideal chemical system where =,
i.e. where leak reactions CD and YX are absent, Eq. (18)
reduces to
AYX Acoupled
= =1 : (19)
ACD ACD
therefore is
6. Minimum entropy generation ACD AYX
Sgen = vCD + vYX
T T
The work of Bejan (1996) suggests that also chemical
Acoupled
energy transfer can be optimized by minimizing the rate + vcoupled : (20)
T
at which entropy is generated during the process. Entropy
generation in our chemical model occurs in three chem- Fig. 9 shows this total entropy generation rate as a func-
ical reactions, and the total rate of entropy generation tion of Acoupled for several values of . Although there are
S. Lems et al. / Chemical Engineering Science 58 (2003) 2001 2009 2007
organic catalysts. In light of this, future processes may rely a unique region of Acoupled where there is a tradeoD between
on either completely organic catalysts or on catalytic organic energy-generation rate and energy e3ciency.
groups located at inorganic surfaces.
Notation
8. Conclusions
A reaction a3nity, J/mol
By applying principles of irreversible thermodynamics ACD a3nity of reaction CD, J/mol
and reaction kinetics to chemical energy transfer, we have Acoupled a3nity of coupled reaction, J/mol
arrived at the following conclusions. AYX a3nity of reaction YX, J/mol
First of all, the optimization of chemical energy trans- MG act activation energy, J/mol
fer shows results that are comparable to those obtained for act
MGleak activation energy of leak reaction, J/mol
heat-driven power plants and other non-chemical systems. act
MGcoupled activation energy of coupled reaction, J/mol
In analog to the latter systems, the chemical system has Mr G Gibbs energy of reaction, J/mol
an optimum output rate of energy at a certain balance be-
thermodynamic e3ciency, dimensionless
tween energy conversion and energy dissipation. However, k0 pre-exponential factor, mol/s
the position of this optimum does not follow from a sim- kinetic parameter, Eq. (11)
ple equipartitioning rule, as is observed in the optimization i stoichiometric coe3cient, dimensionless
of heat-driven power plants. The reason for this signiJcant i chemical potential, J/mol
diDerence is that the rates of chemical reactions nearly al- R gas constant, J=(mol K)
ways respond non-linearly to their a3nity, while heat :ows Sgen entropy generation rate, J=(K s)
are often quite linear functions of temperature diDerence. Sgen; engine internal entropy generation, J=(K s)
Equipartitioning rules do apply when the force:ow rela- Sgen; leak external entropy generation, J=(K s)
tions are near-linear, but fail when these relations are clearly T absolute temperature, K
non-linear. TH temperature of heat source, K
Secondly, the kinetic advantage of the coupled chem- TL temperature of heat sink, K
ical reaction over the leak reactions, indicated by a di- T temperature surroundings, K
mensionless factor , marks out the performance of the v reaction rate, mol/s
chemical system; Higher values of lead to higher thermo-
v forward reaction rate, mol/s
dynamic e3ciencies and to higher work-output rates at
v backward reaction rate, mol/s
every coupled-reaction a3nity (Acoupled ). In addition, the vCD rate of reaction CD, mol/s
optima in e3ciency and in work-output rate are both reached vcoupled rate of coupled reaction, mol/s
at smaller values of Acoupled . Apart from this gradual eDect, vYX rate of reaction YX, mol/s
can also induce a sudden shift in the position of the optima. W lost; engine lost work in heat engine, J/s
This shift re:ects the existence of two energy-conversion W out work-output rate, J/s
strategies, each strategy being superior to the other in its W in work-input rate, J/s
own region of . Below a critical , energy is best trans-
ferred at high rates to keep up with the high levels of energy
dissipation in the leak reactions. Above the critical , how-
Appendix A. Derivation of the optimum work-output re-
ever, energy is best transferred e3ciently at relatively low
quirement
rates, and this yields by far the best performances.
A third conclusion is that the performance of the chem-
The work output rate is given by Eq. (13), and introducing
ical system cannot be optimized by minimizing the total
Eq. (12) gives
rate of entropy generation. Critical review of this optimiza-
tion method reveals that it only works when the work-input W out = (vcoupled vYX )(ACD Acoupled ): (A.1)
rate is constant, i.e. not a function of the optimization vari-
able. If the work-input rate is not constant, the method The rates of the coupled reaction and reaction CD follow
fails because minimum entropy generation rate, maximum from Eq. (7) as
work-output rate, and maximum thermodynamic e3ciency
vcoupled = v coupled (1 eAcoupled =RT );
are then three separate points of operation in energy (A.2)
conversion.
Finally, the model sheds some light on biochemical vYX = v YX (1 eAYX =RT ) = v YX (1 e(Acoupled ACD )=RT ):
the derivative to zero: Finally Eqs. (10) and (11) are used to introduce the kinetic
parameter :
d W out d(ACD Acoupled )
= (vcoupled vYX ) ACD Acoupled
dAcoupled dAcoupled e + 1 eAcoupled =RT 1
RT
d(vcoupled vYX )
+ (ACD Acoupled ) = 0; ACD Acoupled
dAcoupled + 1 e(Acoupled ACD )=RT + 1 = 0:
(A.4) RT
(A.8)
d(ACD Acoupled )
= 1; (A.5) References
dAcoupled
Bejan, A. (1996). Entropy generation minimization, the method of
d(vcoupled vYX ) v coupled Acoupled =RT thermodynamic optimization of 5nite-size systems and 5nite-time
= e
dAcoupled RT processes. New York: CRC Press, Inc.
Chambadal, P. (1957). Les Centrales Nucleaires. Armand Cohin, Paris,
v YX (Acoupled ACD )=RT pp. 4158.
e ; (A.6) De Donder, Th. (1927). LA7nit8e. Paris: Gautier-Villars.
RT Eyring, H. (1935). The activated complex in chemical reactions. Journal
of Chemical Physics, 3, 107.
Introducing Eqs. (A.2), (A.3), (A.5), and (A.6) into Eq. Eyring, H., & Eyring, E. M. (1963). Modern Chemical Kinetics. New
(A.4) and some rearrangement gives York: Reinhold.
Lems, S. (2001). Thermodynamic analysis of intracellular processes,
ACD Acoupled 5nding strategies in cell metabolism for more sustainable processes.
+ 1 e(Acoupled =RT ) 1
v coupled
RT Masters thesis, Laboratory of Applied Thermodynamics and Phase
Equilibria, Delft University of Technology, Delft.
Nelson, L. N., & Cox, M. M. (2000). Lehninger principles of biochemistry
ACD Acoupled
1 e(Acoupled ACD )=RT + 1 = 0:
+ v YX (3rd ed.). New York: Worth Publishers.
RT Westerhof, H. V., & Van Dam, K. (1987). Thermodynamics and control
(A.7) of biological free-energy transduction. The Netherlands: Elsevier.