C Journal of

Carbon Research

Article
Thermochemistry of a Biomimetic and
Rubisco-Inspired CO2 Capture System from Air
Andrew Muelleman, Joseph Schell, Spencer Glazer and Rainer Glaser *
Department of Chemistry, University of Missouri, Columbia, MO 65211, USA;
[email protected] (A.M.); [email protected] (J.S.); [email protected] (S.G.)
* Correspondence: [email protected]; Tel.: +1-573-882-0331

Academic Editor: Enrico Andreoli

Received: 1 May 2016; Accepted: 21 June 2016; Published: 1 July 2016

Abstract: In theoretical studies of chemical reactions the reaction thermochemistry is usually reported
for the stoichiometric reaction at standard conditions (∆G˝ , ∆H˝ , ∆S˝ ). We describe the computation
of the equilibrium concentrations of the CO2 -adducts for the general capture reaction CO2 + Capture
System Õ CO2 -adduct (GCR) and the rubisco-type capture reaction CO2 + Capture System Õ
CO2 -adduct + H2 O (RCR) with consideration of the reaction CO2 (g) Õ CO2 (aq) via Henry’s law.
The resulting equations are evaluated and graphically illustrated as a function of atmospheric CO2
concentration and as a function of temperature. The equations were applied to the thermochemistry
of small molecule rubisco-model reactions and series of additional model reactions to illustrate the
range of the Gibbs free enthalpy for the effective reversible capture and of the reaction entropy for
economic CO2 release at elevated temperature. A favorable capture of free enthalpy is of course a
design necessity, but not all exergonic reactions are suitable CO2 capture systems. Successful CO2
capture systems must allow for effective release as well, and this feature is controlled by the reaction
entropy. The principle of using a two-pronged capture system to ensure a large negative capture
entropy is explained and highlighted in the graphical abstract. It is hoped that the presentation of the
numerical examples provides useful guidelines for the design of more efficient capture systems.

Keywords: carbon capture; CO2 capture from air; temperature dependence of CO2 release;
rubisco model; ab initio theory; thermochemistry; capture reaction Gibbs free enthalpy; capture
reaction entropy

1. Introduction
Continuous atmospheric CO2 tracking started more than 50 years ago with CO2 measurement
at Mauna Loa and resulted in the “Keeling Curve,” the iconic demonstration of the seasonal
variations of CO2 concentrations and the steady rise of the annual average CO2 concentration [1,2].
NOAA’s (National Oceanic and Atmospheric Administration) CarbonTracker [3] employs a global
network of CO2 mole fraction observations to study the CO2 exchange between the biosphere and
the atmosphere as a function of time [4,5]. Comprehensive carbon inventories have been under
development by the US Carbon Cycle Science Program [6] and include space-based CO2 observation
(i.e., Orbiting Carbon Observatory, OCO-2 [7]). While considerable uncertainties remain with regard to
accounting for all CO2 , all reports consistently show that the global atmospheric CO2 concentrations
have been growing steadily, and at Mauna Loa the average annual mean increased from 316.0 ppm
in 1959 to its value of 404.83 ppm at the time of this writing [2]. The Intergovernmental Panel on
Climate Change (IPCC [8]) reported in its fifth assessment report in 2014 (AR5 [9]) an average rate of
increase in CO2 of 1.4 ppm/year. Data by the Energy Information Agency (EIA, [10]) show worldwide
CO2 emissions from the consumption of coal were 13.8 billion metric tons in 2012, up from 8.0 billion
metric tons two decades earlier, and there is no reason to expect this trend to stop any time soon.

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C 2016, 2, 18 2 of 14

The need to communicate climate science and the urgency of addressing the CO2 problem have been
recognized [11–15] but such efforts continue to meet with enormous obstacles [16].
CO2 scrubbing involves the capture of CO2 by a capture system (general capture reaction, GCR),
the release of CO2 from the substrate and its collection, and the long-term CO2 sequestration [17].
CO2 capture from air has been demonstrated [18], it is the pertinent tool to address CO2 emissions
from distributed sources [19–21], and CO2 capture from the air is the method of last resort to combat
excessive atmospheric CO2 concentrations [22–24]. CO2 scrubbing relies on chemical systems for
reversible CO2 capture [25,26] and usually involves carbamic acid formation (i.e., CO2 reaction
with amines [27–29], polyamine-based solid adsorbents [30,31], alkylamine-appended metalorganic
framework [32–34], or diamine-appended metal-organic frameworks [35], and alternative systems [36]).
Biomimetic CO2 capture systems are of interest because they hold the promise to meet both the
thermodynamic and the kinetic requirements for reversible CO2 capture.

CO2 ` Capture System Õ CO2 ´ adduct (GCR)

rCO2 ´ adducts
Keq pGCRq “
rCapture Systems ˆ rCO2 s
CO2 ` Carbonyl¨ H2 N ´ ppeptideq ´ MgL2 ¨ OH2 Õ CO2 ´ adduct ` H2 O (PCR)

CO2 ` Capture System Õ CO2 ´ adduct ` H2 O

rCO2 ´ adducts ˆ rH2 Os
Keq pRCRq “
rCapture Systems ˆ rCO2 s
We have been interested in the development of rubisco-based biomimetic systems for reversible
CO2 capture from air. Our design of the chemical CO2 capture and release systems is informed by the
understanding of the binding of the activator CO2 (A CO2 ) in rubisco (Figure 1) and the general strategy
has been described [37,38]. Rubisco (ribulose 1,5-bisphosphate carboxylase/oxygenase, RuBisCO)
catalyzes the addition of CO2 and water to RuBP (d-ribulose 1,5-bisphosphate) in the photosynthetic
carbon assimilation via the Calvin-Bassham-Benson cycle, and results in two molecules of 3-PGA
(3-phospho-d-glycerate) and 0.5 O2 [39,40]. Nearly all carbohydrate production in the biosphere
depends on rubisco catalysis and rubisco is the most abundant protein on Earth. Form I rubisco
contains eight large (L) and eight small (S) subunits, and the crystal structure of Spinacia oleracea [41,42]
provided an early example of a hexa-decameric rubisco [43]. Form II rubisco lacks small subunits,
generally occurs as L2 , and is exemplified by the bacterial rubisco of Rhodospirillum rubrum [44].
The mechanism of rubisco catalysis has been studied in detail [45,46] and these studies have established
that rubisco must be activated by carbamylation of active-site lysine (Lys) with an activator CO2 (A CO2 ).
The carbamate formed is stabilized both by complexation to Mg2+ and by NH¨ ¨ ¨ OC hydrogen-bonding
(Figure 1) and, importantly, the rubisco A CO2 capture (RCR) occurs with the release of a water molecule
from the capture system.
In theoretical studies of reaction thermochemistry one usually computes the reaction enthalpy
∆H and the reaction entropy ∆S˝ for the stoichiometric reaction at standard conditions (1 atm,
˝

25 ˝ C) and determines the reaction Gibbs free enthalpy via ∆G˝ = ∆H˝ ´ T˝ ¨ ∆S˝ . This knowledge
then allows for the computation of equilibrium concentrations, although this step is not usually
applied in theoretical studies. For reactions with a severely limited reagent, one needs to consider the
consequences of the non-stoichiometry on product formation. With an atmospheric CO2 concentration
of about 400 ppm, questions about the equilibrium concentration of CO2 capture reactions have been
asked frequently and they are entirely warranted. Hence, in this paper, we describe the determination
of CO2 capture equilibria as a function of CO2 concentration. In addition, we describe temperature
dependence of the CO2 capture equilibria with a focus on the importance of the reaction entropy for
effective CO2 release at elevated temperature.
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Figure 1.
1. CO
CO2 capture in the active site of rubisco.
Figure 2 capture in the active site of rubisco.

2. Results and Discussion

2. Results and Discussion
2.1. Capture
2.1. Capture Reaction
Reaction Systems
Systems Studied
Studied
We analyzed
We analyzed the the thermochemistry
thermochemistry of of aa rubisco-based
rubisco-based small
small molecule
molecule model
model ofof the
the formation
formation of of
N-methylcarbamic acid (NMCA) by addition of methylamine (CH 3NH2) to CO2, considering substrate
N-methylcarbamic acid (NMCA) by addition of methylamine (CH3 NH2 ) to CO2, considering substrate
and product
and product stabilization
stabilization by by anan active-side
active-side carbonyl
carbonyl model
model andand complexation
complexation by by aa model
model metal
metal
complex ML 2 [37]. The model system is described by 14 reactions and the thermochemistry was
complex ML2 [37]. The model system is described by 14 reactions and the thermochemistry was
determined at
determined at the
the B3LYP/6-31G*
B3LYP/6-31G* level level for
for the
thenatural
naturalcase
caseofofmagnesium
magnesiumMM 2+2+== Mg
Mg2+2+. Reaction R1 is
. Reaction R1 is
the formation of NMCA (H 3CNHCOOH) by addition of methylamine to CO2 in the gas phase.
the formation of NMCA (H3 C´NH´CO´OH) by addition of methylamine to CO2 in the gas phase.
Three effects
Three effects of
of the
the environment
environment need need toto be
be considered
considered in in the
the active
active site
site of
of rubisco
rubisco (Figure
(Figure 1)1) and
and
these are
these are (A)
(A) the
the stabilization
stabilization of of the
the product
product by by hydrogen-bonding
hydrogen-bonding between between NMCANMCA and and aa model
model
carbonyl compound; (B) the complexation of NMCA by a model metal
carbonyl compound; (B) the complexation of NMCA by a model metal complex ML2 ; and (C) the complex ML 2; and (C) the

forced replacement
forced replacement of of ligand
ligand water
water byby CO
CO2 at at the
the metal
metal center.
center.
2
Importantly,the
Importantly, thecomplexation
complexationof ofCO
CO2to tothe
the metal
metalcation
cationM M2+
2+ requires the replacement of a water
requires the replacement of a water
2
molecule, and
molecule, and our
our analysis
analysis showed
showedthat thatthis
thisH H2O/CO
O/CO2 replacement
replacement is
is an
an essential
essential feature
feature ofof rubisco
rubisco
2 2
thermochemistry.The
thermochemistry. Theexchange
exchangeof ofaaligand
ligandwater
watermolecule
moleculeby byaa CO
CO2 molecule (reaction R10) is highly
2 molecule (reaction R10) is highly
endergonic and this H 2O/CO2 replacement penalty is required to lower the overall exergonicity of the
endergonic and this H2 O/CO2 replacement penalty is required to lower the overall exergonicity of
CO2CO
the capture reaction and to allow overall reversibility. Reaction R14 models the capture of CO2 and
2 capture reaction and to allow overall reversibility. Reaction R14 models the capture of CO2
the addition
and the additionof the Mg
of the Mg-complexed
2+ 2+
-complexed COCO2 to a pre-positioned, carbonyl-aggregated methylamine
2 to a pre-positioned, carbonyl-aggregated methylamine
CH 3NH2·(A/K) to form the Mg2+2+
CH NH ¨ (A/K) to form the Mg -complexed -complexed andandcarbonyl-aggregated
carbonyl-aggregatedNMCA, NMCA,(A/K)·NMCA·ML
(A/K)¨ NMCA¨ ML 2.
.
3 2 2

CO2 + CH3NH2 ⇆ NMCA (R1)

CO2 ` CH3 NH2 Õ NMCA (R1)

2 + CO2 + CH3NH2·FA ⇆ 17a + H2O (R14a)

O¨2O·MgL
H2H MgL2 ` CO2 ` CH3 NH2 ¨ FA Õ 17a ` H2 O (R14a)

H2H
O¨2O·MgL
MgL2 `
2 +CO
CO22` CH33NH
+ CH ¨ Ac⇆Õ
NH22·Ac + H`2OH2 O
21a21a (R14b)
(R14b)
CO2 pgq Õ CO2 paqq (R15)
CO2(g) ⇆ CO2(aq) (R15)
We evaluated the RCR-reaction R14 with the model carbonyl formaldehyde (FA, R14a) and
We(Ac,
acetone evaluated the RCR-reaction
R14b), respectively. R14 with
Molecular theofmodel
models the COcarbonyl formaldehyde (FA, R14a) and
2 -adducts 17a (R14a) and 21a (R14b) are
acetone (Ac, R14b), respectively. Molecular models of the CO2-adducts 17a (R14a) and 21a (R14b) are
shown in Figure 2, and the associated thermochemical parameters are listed in Table 1.
shown in Figure 2, and the associated thermochemical parameters are listed in Table 1.
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R = H: 17a
17a 21a
R = CH3: 21a

Figure2.2. Molecular
Figure Molecular model
modelof ofaggregates
aggregates17a
17aand
and21a
21aformed
formedbetween
betweenthe
themagnesium
magnesiumformate
formateMgL
MgL22
complexed trans-trans
complexed trans-trans isomer
isomer ofof N-methylcarbamic
N-methylcarbamic acid
acid and
and model
model carbonyl
carbonyl formaldehyde
formaldehyde (FA)
(FA) or
or
acetone (Ac), respectively. (Ball and Bond Type models are shown and color indicates elements:
acetone (Ac), respectively. (Ball and Bond Type models are shown and color indicates elements: oxygen:
oxygen:
red; red; nitrogen:
nitrogen: blue;grey;
blue; carbon: carbon: grey; hydrogen:
hydrogen: yellow; magnesium:
yellow; magnesium: lime). lime).

Table1.1.Thermochemical
Table Thermochemicaldata
datafor
forcapture
capturesystems.
systems.11

Fraction CO2-Adduct at [CO2] = 400 ppm

Reaction ΔG° ΔH° ΔS° Fraction CO2T°
-Adduct
Reaction ∆G˝ ∆H ˝ ∆S˝ T° + 20 at [CO2 ]T°= +400
40 ppm
R1 4.09 −2.02 −20.49 T˝ T ˝ + 20 T ˝ + 40
R1R14a 4.09−6.59 ´2.02
−17.26 ´20.49
−35.79 0.0163 0.00159 0.000202
R14a ´6.59 ´17.26 ´35.79 0.0163 0.00159 0.000202
R14b
R14b ´5.54−5.54 −17.72
´17.72 −40.85
´40.85 0.00281
0.00281 0.000257
0.000257 0.0000313
0.0000313
R14h
R14h ´9.00−9.00 −19.67
´19.67 −35.79
´35.79 0.4920.492 0.06760.0676 0.00737
0.00737
HR1a
HR1a ´6.59−6.59 ´15.00
−15.00 ´28.21
−28.21 0.0163
0.0163 0.00204
0.00204 0.000320
0.000320
HR1b ´6.59 ´20.00 ´44.98 0.0163 0.00120 0.000118
HR1b
HR1c ´6.59−6.59 −20.00
´25.00 −44.98
´61.75 0.0163
0.0163 0.00120
0.000705 0.000118
0.0000435
HR2a
HR1c ´9.00−6.59 −25.00
´15.00 −61.75
´20.12 0.492
0.0163 0.106
0.000705 0.0184
0.0000435
HR2b ´9.00 ´20.00 ´36.89 0.492 0.0654 0.00685
HR2a −9.00 −15.00 −20.12 0.492 0.106 0.0184
HR2c ´9.00 ´25.00 ´53.66 0.492 0.0395 0.00254
HR2b
HR3a −9.00
´11.00 −20.00
´17.00 −36.89
´20.12 0.4920.966 0.06540.738 0.00685
0.269
HR3b
HR2c ´11.00
−9.00 ´22.00
−25.00 ´36.89
−53.66 0.4920.966 0.03950.623 0.119
0.00254
HR3c ´11.00 ´27.00 ´53.66 0.966 0.493 0.0499
HR3a −11.00 −17.00 −20.12 0.966 0.738 0.269
1 Gibbs free enthalpy ∆G˝ and enthalpy ∆H˝ in kcal/mol. Entropy ∆S˝ in cal/(mol¨ K).
HR3b −11.00 −22.00 −36.89 0.966 0.623 0.119
HR3c
2.2. Equilibrium −11.00 with−27.00
Concentrations −53.66
Non-Stoichiometric0.966
Conditions0.493 0.0499
1 Gibbs free enthalpy ΔG° and enthalpy ΔH° in kcal/mol. Entropy ΔS° in cal/(mol·K).

The calculation of thermodynamic data for a given reaction with ab initio methods uses
stoichiometric concentrations
2.2. Equilibrium Concentrationsofwith
the reagents. In the caseConditions
Non-Stoichiometric of passive carbon capture, such an assumption
does not accurately depict the relative concentrations of the reagents. Passive capture systems must
The calculation of thermodynamic data for a given reaction with ab initio methods uses
operate at low pressures of CO2 , including the current atmospheric concentration (~400 ppm) [47].
stoichiometric concentrations of the reagents. In the case of passive carbon capture, such an
assumption does not accurately depict the relative rCO2concentrations
paqqs of the reagents. Passive capture
KH “ (1)
systems must operate at low pressures of CO 2, including
PCO2 the current atmospheric concentration (~400
ppm) [47].
Also, Henry’s Law must be considered CO (for )aqueous carbon capture systems, because only
=
dissolved CO2 is available for binding. Henry’s Law describes the proportion of gaseous CO2 that (1)
enters the aqueous phase at equilibrium, illustrated in reaction (R15) and described by Equation (1).
KH (T)Also, Henry’s
is constant forLaw must
a given gasbeand
considered for aqueousfor
a given temperature; carbon
CO2 at capture systems, because
room temperature only
this value
dissolved
has CO2 is available
been experimentally for binding.
determined Henry’s
to be Law =describes
KH (298.15) the[48].
K0H = 0.034 proportion of gaseous
Using Henry’s Law CO
and2 that
the
atmospheric pressure of CO2 , it is then simple to determine an approximate concentration of CO2(1).
enters the aqueous phase at equilibrium, illustrated in reaction (R15) and described by Equation in
KH(T)
the is constant
aqueous phasefor
ofaagiven gascapture
passive and a given
system.temperature; for CO2 at room temperature this value has
been experimentally determined to be KH(298.15) = = 0.034 [48]. Using Henry’s Law and the
atmospheric pressure of CO2, it is then simple to determine an approximate concentration of CO2 in
the aqueous phase of a passive capture system.
C 2016, 2, 18 5 of 14
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In this work, we primarily focus on the simple capture reactions (R1) and the rubisco capture
reactions (R14). The product formation can be calculated using the equations for the equilibrium
In this
constants Keqwork, we primarily
for reactions (GCR)focus on the respectively.
and (RCR), simple capture reactions
Defining the(R1) and the rubisco
concentration capture
of the capture
reactions (R14). The product formation can be calculated using the equations for
system at equilibrium [CS] = [CS]0 − [CO2-CS], where [CO2-CS] is the concentration of the CO2-adduct the equilibrium
constants
formed andKeq for0 reactions
[CS] (GCR)
is the initial and (RCR),ofrespectively.
concentration Definingwe
the capture system, the concentration
obtain equationsof(2-GCR)
the capture
and
system
(2-RCR).at equilibrium [CS] = [CS]0 ´ [CO 2 -CS], where [CO 2 -CS] is the concentration of the CO 2 -adduct
formed and [CS]0 is the initial concentration of the capture system, we obtain equations (2-GCR)
× × ×
and (2-RCR). [CO2 -CS] = (2-GCR)
1 × ×
rCSs 0 ˆ Keq ˆ PCO2 ˆ K H
rCO2 ´ CSs “ (2-GCR)
1 ` Keq ˆ PCO2 ˆ K H
× × ×
CO2 = rCSs ˆ K ˆ P ˆ KH (2-RCR)
rCO2 s “ 55.5 × 2×
0 eq CO
(2-RCR)
55.5 ` Keq ˆ PCO2 ˆ K H
CO -CS ( ∆ / )
rCO22´ CSs=
CS “ K H× ˆ PCO× 2
ˆ ep´∆G{RTq (3-GCR)
(3-GCR)
rCSs

rCO
[CO2 2´ CSs
-CS] K H× ˆ PCO×2 ˆ( e∆p´/∆G){RTq
=“ (3-RCR)
(3-RCR)
rCSs
[CS] 55.5
55.5
The isotherms in Figure 3 show the concentration of the CO -adduct formed [CO -CS] as a
The isotherms in Figure 3 show the concentration of the CO22-adduct formed [CO22-CS] as a
function of the CO pressure. This relationship produces isothermal curves with their asymptotic
function of the CO22 pressure. This relationship produces isothermal curves with their asymptotic
boundaries determined by the initial concentration of the capture system.
boundaries determined by the initial concentration of the capture system.

(a) (b)

(c) (d)
Figure 3. Equilibrium concentrations of complexed product of a general capture reaction (GCR) (left)
Figure 3. Equilibrium concentrations of complexed product of a general capture reaction (GCR)
and a rubisco-type capture reaction (RCR) (right) at five temperatures from 278.15 to 318.15 K. The
(left) and a rubisco-type capture reaction (RCR) (right) at five temperatures from 278.15 to 318.15 K.
color of the central curve (298.15 K) corresponds to the same system in Figures 3 and 4. Panels (a) and
The color of the central curve (298.15 K) corresponds to the same system in Figures 3 and 4. Panels
(b) describe the thermochemistry of R14a with ΔG° = −6.59 kcal/mol, ΔH° = −17.26 kcal/mol, and ΔS°
(a) and (b) describe the thermochemistry of R14a with ∆G˝ = ´6.59 kcal/mol, ∆H˝ = ´17.26 kcal/mol,
= −35.81˝ cal/(mol·K). Panels (c) and (d) describe the thermochemistry of R14h with ΔG° = −9.00
and ∆S = ´35.81 cal/(mol¨ K). Panels (c) and (d) describe the thermochemistry of R14h with
kcal/mol,
∆G˝ = ´9.00ΔH°kcal/mol,
= −19.67 kcal/mol, and ΔS°
∆H˝ = ´19.67 = −35.79and
kcal/mol, cal/(mol·K). Solid cal/(mol¨
∆S˝ = ´35.79 lines wereK).
computed with
Solid lines T-
were
dependence of Henry’s Law and dashed lines were computed without.
computed with T-dependence of Henry’s Law and dashed lines were computed without.
 (Figure 3d, green curve) and a very reasonable capture fraction of 0.492 (Table 1) at [CO2] = 400 ppm.
Temperature affects the curvature of the fraction (CO2-adduct) = f([CO2]) isotherms in Figure 3
and we will discuss the T-dependence in more detail below (see Section 2.3). Instead of the fraction (CO2-
adduct), Figures 4 and 5 show the ratios [CO2-CS]/[CS] as a function of [CO2]. The ratios were computed
with equations 3-GCR and 3-RCR, where R is the gas constant (1.9858775 cal·mol−1·K−1), ΔG is the Gibbs
C 2016, 2, 18 6 of 14
Free Enthalpy of the capture reaction at T, and ΔG = ΔG° for the special case of T = T°. This ratio shows
a linear dependence on the CO2 pressure, and temperature affects the slope (but not the curvature).

C 2016, 2, 18 6 of 14

The fraction of CO2-adduct differs greatly in magnitude depending on the application of the GCR
or RCR equations. The same thermochemical parameters afford much higher fractions computed with
the GCR equation than with the correct RCR equation (Figure 3). The fractions computed with the
RCR equations for reactions R14a (red) and R14b (blue) at [CO2] = 400 ppm are listed in Table 1, and
the respective values of 0.016 and 0.003 are very small. Obviously, our simplified theoretical model
produces ΔG° values that are not exergonic enough. Hence, we also studied the hypothetical reaction
(a) (b)
R14h with ΔG° = −9 kcal/mol. For this model system, we set ΔS° (R14h) = ΔS° (R14a) and obtain ΔH°
(R14h) = −19.67
Figure kcal/mol.
4. Carbon With at
capture R14h,298.15we achieve
K for two a much
carbon more effective
capture capture
systems at room
at near temperature
atmospheric
4. Carbon capture
Figureconcentrations. at 298.15 K foroftwo carbon capture systems at near atmospheric concentrations.
(Figure 3d, green curve) andenthalpies
Gibbs free a very reasonable capture
ΔG° = −5.54 fraction
kcal/mol ofblue),
(R14b, 0.492ΔG° (Table 1) atkcal/mol
= −6.59 [CO2] =(R14a,
400 ppm.
Gibbsred),
free and
enthalpies
Temperature of ∆G
ΔG° =affects
−9.00
˝
the =curvature
kcal/mol ´5.54(R14h, kcal/mol
green). (R14b,
Plots
of the fraction blue),
for (CO ∆G
GCR2-adduct)
are
˝ = ´6.59 kcal/mol (R14a, red), and
shown = in (a) and
f([CO plots for the
2]) isotherms inRCR
Figure 3
∆G ˝
and =we ´9.00
are shown
will kcal/mol
in (b).
discuss (R14h,
achievegreen).
theToT-dependence Plots
a significant
in more for GCR
capture
detail ratio are
below shown
in(see
the in2.3).
RCR system
Section (a) Instead
and plots
requires ofatheforfraction
the RCR
significantly (COare
2-
shown
adduct),in Figures
more (b). To 4achieve
exergonic capture
and a reaction;
5 show significant capture
i.e., green
the ratios ratio
in (b).
[CO2-CS]/[CS] Theinas the RCRaxis
secondary
a function system (b) requires
ofin[CO allows
2]. The for athe
significantly
ratios recognition
were more
computed
with of
exergonic the much3-GCR
capture
equations diminished
reaction;
and i.e.,capture
3-RCR,green ratios
where Rfor
in (b). the secondary
isThe
the less constant
gas exergonicaxisreactions (blue
in (b) allows
(1.9858775 cal·mol and
for−1·Kred).
the Theislinear
recognition
−1), ΔG of the
the Gibbs
Free functions are as follows: (a) Blue;forythe
=at3.91 × 10 -4x, Red; y = 2.30·× 10-3x; (b) Blue; y = 7.05 × 10-6x, Red; y
much Enthalpy
diminished of the capture
capture reaction
ratios T,less
and ΔG = ΔG°reactions
exergonic for the special
(bluecaseandofred).
T = T°.TheThis ratio
linear shows
functions
a linear
are × 10-5x, Green;
as=follows:
4.15
dependence on ythe
(a) Blue; y= =2.42
CO ×2 pressure,
3.91 10-3x. ´4 and temperature affects
ˆ 10 x, Red; y = 2.30¨ ˆ 10´3 x; the(b)
slope
Blue; (but
y =not theˆcurvature).
7.05 10´6 x, Red;
´5
y = 4.15 ˆ 10 x, Green; y = 2.42 ˆ 10 x. ´3

The fraction of CO2 -adduct differs greatly in magnitude depending on the application of the GCR
or RCR equations. The same thermochemical parameters afford much higher fractions computed with
the GCR equation than with the correct RCR equation (Figure 3). The fractions computed with the
RCR equations for reactions R14a (red) and R14b (blue) at [CO2 ] = 400 ppm are listed in Table 1, and
the respective values of 0.016 and 0.003 are very small. Obviously, our simplified theoretical model
produces ∆G˝ values that are not exergonic enough. Hence, we also studied the hypothetical reaction
R14h with ∆G˝ = ´9 kcal/mol. For this model system, we set ∆S˝ (R14h) = ∆S˝ (R14a) and obtain ∆H˝
(R14h) = ´19.67 kcal/mol. With R14h, we achieve a much more effective capture at room temperature
(a) (b)
(Figure 3d, green curve) and (a) a very reasonable capture fraction of 0.492 (b)(Table 1) at [CO2 ] = 400 ppm.
Figure 5. Carbon
Temperature releasecurvature
at 348.15 K of
(= T° + 50) for two(CO
carbon-adduct)
capture systems at near atmosphericin Figure 3
Figure 4. affects
Carbon thecapture at 298.15 the
K forfraction
two carbon = f([CO
2capture systems 2 ]) isotherms
at near atmospheric
concentrations. Color indicates reaction thermochemical parameters; blue curves (R14b), red curves
and we will discuss the
concentrations. T-dependence
Gibbs free enthalpies in
of ΔG°more detail
= −5.54 below
kcal/mol (see
(R14b, Section
blue), ΔG° = 2.3). Instead
−6.59 kcal/mol of the fraction
(R14a,
(R14a), and green curves (R14h). The linear functions are as follows: (a) GCR: y = 1.66 × 10-6x (blue);
(CO2 -adduct), Figures
red), and ΔG° =4−9.00
and 5 show
kcal/mol the
(R14h, ratios
green).[COPlots2 -CS]/[CS]
for GCR as a
are shown function
in -6(a) andof
1.10 × 10 x (red). (b) RCR: y = 3.02 × 10 x (blue); 1.99 × 10 x (red); 6.48 × 10 x (green).
-5 -8 -7 [CO
plots for2 ].
theThe
RCRratios were
computedare shown
with in (b). To3-GCR
equations achieveand
a significant
3-RCR,capture
whereratio R isinthe
thegas
RCRconstant
system requires
(1.9858775 cal¨ mol´1 ¨ K´1 ),
a significantly
more exergonic capture reaction; i.e., green in (b). The secondary axis in (b) allows
∆G is the Gibbs Free Enthalpy of the capture reaction at T, and ∆G = ∆G˝ for for thethe recognition
special case of T = T˝ .
of the much diminished capture ratios for the less exergonic reactions (blue and red). The linear
This ratio shows a linear dependence on the CO pressure, and -3temperature affects-6the slope (but not
2 Red;
functions are as follows: (a) Blue; y = 3.91 × 10-4x, y = 2.30·× 10 x; (b) Blue; y = 7.05 × 10 x, Red; y
the curvature).
= 4.15 × 10-5x, Green; y = 2.42 × 10-3x.

(a) (b)
Figure 5. Carbon release at 348.15 K (= T° + 50) for two carbon capture systems at near atmospheric
Figure 5. Carbon release at 348.15 K (= T˝ + 50) for two carbon capture systems at near atmospheric
concentrations. Color indicates reaction thermochemical parameters; blue curves (R14b), red curves
concentrations.
(R14a), and Color indicates
green curves reaction
(R14h). thermochemical
The linear functions are as parameters; blue curves
follows: (a) GCR: y = 1.66 (R14b), red curves
× 10-6x (blue);
(R14a),1.10
and green curves (R14h). The linear functions are as follows: (a) GCR: y = 1.66 ˆ 10 ´6 x (blue);
× 10 x (red). (b) RCR: y = 3.02 × 10 x (blue); 1.99 × 10 x (red); 6.48 × 10 x (green).
-5 -8 -7 -6

1.10 ˆ 10´5 x (red). (b) RCR: y = 3.02 ˆ 10´8 x (blue); 1.99 ˆ 10´7 x (red); 6.48 ˆ 10´6 x (green).
C 2016, 2, 18 7 of 14

The Gibbs free enthalpy of the capture reaction obviously will vary with temperature because
of the entropy term, ∆G = ∆H ´ T¨ ∆S. The reaction enthalpy ∆H(T) and reaction entropy ∆S(T)
depend on temperature only modestly and, for the temperature variations considered here, they can
be approximated very well by ∆H(T) = ∆H˝ and ∆S(T) = ∆S˝ . However, in our aqueous system
temperature also significantly affects Henry’s constant. This variation is described by the van’t Hoff
equation (Equation (4)), where the change in enthalpy of dissolution is a constant for a given gas.
For CO2 the value is –∆sol H/R = 2400 K. With this value, Equation (5) can be used to determine the
value of the Henry’s constant at temperature T for CO2 .

dlnK H ´∆sol H
“ (4)
d p1{Tq R
ˆ ˆ ˙˙
´∆sol H 1 1
K H pTq “ K oH ˆ exp ´ ˝ (5)
R T T
For –∆sol H/R > 0, it is clear that CO2 will be better solvated at low temperatures and less solvated
at temperatures higher than 298.15 K. This drives capture to be more effective at lower temperatures
and release to be more effective at higher temperatures. The consequences of the T-dependence of
Henry’s constant are illustrated for specific cases in Figure 3, where solid lines were computed with
T-dependence of Henry’s Law and dashed lines without. In every panel, the dashed curves always are
closer to the T˝ -curve than the solid curves, that is, the load difference will always be increased by the
T-dependence of Henry’s constant.

2.3. Temperature Dependence of Capture Systems: Loading and Unloading

This illustration in Figure 6 is a rough schematic to consider the scale of the CO2 capture in a
gedankenexperiment (German: thought experiment). This apparatus is comprised of several square
trays containing thin layers of aqueous capture solution. In order to capture large amounts of CO2 ,
the most important aspect is the volume of the capture system solution (CSS). To illustrate that
a large volume is desired as well as a large surface area, a rack of shallow baths of solution was
chosen to balance these two goals in a simple way. These thin layers are an attempt to acknowledge
that the diffusion is a relevant and an important factor, but the schematic system is not optimized
for diffusion because the main purpose of the gedankenexperiment is the thermodynamic analysis
of slow processes. Because capture from ambient air occurs at very high dilutions of CO2 , it will
not be a fast capture regardless. Of course, for fast capture at concentrated sources, the amount of
CO2 captured is controlled by kinetics and sophisticated chemical engineering solutions have been
described that include more complicated gas/liquid contactor systems [49–52] and counter-current
flow systems [53]. These systems vastly increase surface area-to-volume ratios and provide for surface
renewal opportunities and facile gas diffusion. However, for passive capture from air the simplified
apparatus of Figure 6 suffices to obtain a rough estimate of the amount of CO2 that would be collected
per load cycle.
Load “ FWpCO2 q ˆ rCO2 ´ CSs400 ˆ VCSS (6)

The load is determined by the volume of the capture system solution, the initial concentration
of the amine capture system, and the temperature of the aqueous capture system. The Load can be
calculated simply using Equation (6), where Load is the mass of captured CO2 in g, FW(CO2 ) is the
formula weight for CO2 , 44.01 g/mol, [CO2 -CS]400 is the equilibrium concentration of product (mol/L)
when the partial pressure of CO2 is 400 ppm, and V CSS is the volume of the capture system solution
(L). For an ideal capture system, the load should be highly dependent on the temperature so that
T-variation may afford release under economic conditions. The fraction captured per cycle can be
determined by comparison of the load data at capture and release temperatures (Table 1).
For a numerical illustration, we consider the trays of the apparatus to have a surface areas of 1 m2
and to hold a solution with a depth of 2.5 cm. For a standard system of 10 layers of these trays, this
C 2016, 2, 18 8 of 14

example results in a total solution volume of 250 L. Assuming an initial concentration of the capture
system solution [CS]0 = 0.1 M, the load is calculated using Equation (6). To find the concentration of
the product, the initial concentration of the capture system solution is multiplied by the fraction of
CO2 -adduct reported in Table 1. The amount of CO2 collected in one capture cycle, the cycle load,
equals the difference of the loads at the capture and release temperatures. With apparatus parameters
being equal, the cycle load parallels the difference in the CO2 -adduct fractions at capture and release
temperatures (cycle load fraction). In the case of capture system R14h, the free enthalpy is low enough
to ensure binding at T˝ and the data in Table 1 show the fractions of CO2 -adduct to be 0.492 (T˝ ),
0.068 (T˝ + 20), and 0.007 (T˝ + 40). The fractions show that most CO2 will be released when the
temperature is raised by 20˝ , and that nearly all of the CO2 will be released when the temperature
is raised by 40˝ . The amount of CO2 collected per cycle for a capture temperature of T˝ and release
temperatures
C 2016, 2, 18 of T˝ + 20 and T˝ + 40 are 0.47 kg and 0.53 kg, respectively. 8 of 14

Figure6.
Figure 6. Schematic
Schematic diagram
diagram of
ofthe
thecarbon
carboncapture
captureapparatus.
apparatus.

For a numerical illustration, we consider the trays of the apparatus to have a surface areas of 1
2.4.2 Variations of Thermodynamic Parameters—Guidelines for Capture System Design
m and to hold a solution with a depth of 2.5 cm. For a standard system of 10 layers of these trays,
this We modeled
example threeinsets
results of hypothetical
a total solution volumereactions
of HR1´HR3
250 L. Assumingto explore the effectiveness
an initial concentration of capture
of the
and
capture system solution [CS]0 = 0.1 M, the load is calculated using Equation (6). To find sets
release in dependence of the Gibbs free enthalpy and the capture reaction entropy (Table 1). The the
differ in the Gibbs
concentration of thefreeproduct,
enthalpythe with ∆G˝concentration
initial = ´6.59 kcal/molof thefor HR1 (as
capture for R14a),
system ∆G˝is=multiplied
solution ´9 kcal/mol by
for
theHR2,
fractionandof∆GCO˝ 2-adduct
= ´11 kcal/mol
reported for HR3. 1.Within
in Table each set,
The amount we2 vary
of CO ∆H˝ in
collected inone
steps of 5 kcal/mol.
capture cycle, the
For
cycleHR1 andequals
load, HR2, we the use ∆H˝ values
difference of theofloads
´15, at theand
´20, ´25 kcal/mol,
capture and release respectively,
temperatures. the ∆S
andWith ˝ values
apparatus
follow.
parameters The being
systems HR3the
equal, were constructed
cycle to share
load parallels the ∆S˝ values
the difference in the COwith HR2 and
2-adduct the ∆Hat˝ capture
fractions values
follow. Withtemperatures
and release these parameters, (cyclewe used
load equation
fraction). In 2-RCR
the casetoofcompute
capture the fractions
system R14h,of CO
the free
2 -adduct at
enthalpy
[CO ] = 400 ppm and T ˝ , T ˝ + 20, and T˝ + 40, and the results are listed in Table 1.
is low
2 enough to ensure binding at T° and the data in Table 1 show the fractions of CO2-adduct to be
0.492Reaction HR1
(T°), 0.068 (T°is+ not
20),sufficiently
and 0.007 (T° exergonic
+ 40). Thetofractions
produce show
adequate that capture
most COand Table
2 will 1 showswhen
be released that
all
thefractions
temperatureare relatively
is raised by low.
20°,Reactions HR2 and
and that nearly HR3,
all of with
the CO their
2 will behigher
released binding
when thefreetemperature
enthalpies,
demonstrate
is raised by 40°.adequate capture,ofand
The amount COthese systems
2 collected perare illustrated
cycle in Figure
for a capture 7.
temperature of T° and release
Figure 7 shows
temperatures of T° +the20fractions
and T° + of 40CO
are2 -adduct remaining
0.47 kg and 0.53 kg,bound at T˝ + 40 for the series of reactions
respectively.
HR2 and HR3, and this figure reveals the important role of entropy in the release process. As the
2.4. Variations
reaction becomes of Thermodynamic
more exentropic, Parameters—Guidelines
the cycle yield improves for Capture System
in all cases, butDesign
the capture effectiveness
is more complicated. For the most exentropic reaction of the HR2 series (HR2c), the fraction of
We modeled three sets of hypothetical reactions HR1−HR3 to explore the effectiveness of capture
CO2 -adduct remaining at T˝ + 40 is 0.003 and the unloading is highly effective. Even for the system
and release in dependence of the Gibbs free enthalpy and the capture reaction entropy (Table 1). The
HR2a, with its exentropicity mirroring that of the GCR R1, the unloading remains efficient: the fraction
sets differ in the Gibbs free enthalpy with ΔG° = −6.59 kcal/mol for HR1 (as for R14a), ΔG° = −9
remaining is only 0.018 and the cycle load difference relative to HR2c is small (3.3%). Comparison of
kcal/mol for HR2, and ΔG° = −11 kcal/mol for HR3. Within each set, we vary ΔH° in steps of 5
the HR2 series (Figure 7a) shows that at atmospheric pressure, the difference in capture due to entropy
kcal/mol. For HR1 and HR2, we use ΔH° values of −15, −20, and −25 kcal/mol, respectively, and the
is functionally low.
ΔS° values follow. The systems HR3 were constructed to share the ΔS° values with HR2 and the ΔH°
In the more exergonic series of hypothetical reactions (HR3), the cycle load efficiency increases as
values follow. With these parameters, we used equation 2-RCR to compute the fractions of CO2-
with HR2 as the system becomes more exentropic. However, with the more exergonic reaction HR3,
adduct at [CO2] = 400 ppm and T°, T° + 20, and T° + 40, and the results are listed in Table 1.
Reaction HR1 is not sufficiently exergonic to produce adequate capture and Table 1 shows that
all fractions are relatively low. Reactions HR2 and HR3, with their higher binding free enthalpies,
demonstrate adequate capture, and these systems are illustrated in Figure 7.
Figure 7 shows the fractions of CO2-adduct remaining bound at T° + 40 for the series of reactions
HR2 and HR3, and this figure reveals the important role of entropy in the release process. As the
C 2016, 2, 18 9 of 14

the effect of entropy is drastically enhanced. Reaction HR3a is shown to have a fraction of CO2 -adduct
of 0.269 at T˝ + 40 compared to HR3b with a fraction of 0.119 remaining. This corresponds to a 21.5%
increase in cycle load for the more exentropic reaction. Further, the fraction of CO2 -adduct remaining
for HR3c at the same temperature is 0.050. This is an 8.1% increase over HR3b and a 31.4% increase
over HR3a. As illustrated by the increase in cycle load percentage across each series, the entropy effects
C 2016, 2, 18 9 of 14
for the more exergonic HR3 system are enhanced by a factor of nearly 10 over HR2.

(a) (b)

Figure 7. Fraction of CO2-adduct remaining in capture solution at equilibrium at 338.15 K (= T°˝ + 40)
Figure 7. Fraction of CO2 -adduct remaining in capture solution at equilibrium at 338.15 K (= T + 40)
for the RCR-type reactions (a) HR2 with ΔG° = −9 kcal/mol and (b) HR3 with ΔG° = −11 kcal/mol.
for the RCR-type reactions (a) HR2 with ∆G˝ = ´9 kcal/mol and (b) HR3 with ∆G˝ = ´11 kcal/mol.
Reactions HR2 and HR3 are shown with entropies ΔS° of˝−20.12 (blue), −36.89 (yellow), and −53.66
Reactions HR2 and HR3 are shown with entropies ∆S of ´20.12 (blue), ´36.89 (yellow), and
cal/(mol·K) (red).
´53.66 cal/(mol¨ K) (red).

In the more exergonic series of hypothetical reactions (HR3), the cycle load efficiency increases
as withAfter HR2 studying these hypothetical
as the system becomes more systems, it becomes
exentropic. However, pertinent
with the to determine
more exergonic whichreaction
would
HR3, the effect of entropy is drastically enhanced. Reaction HR3a is shown to have a fraction ofshown
provide the best capture and the capture temperature plays an important role. We have already CO2-
that ∆Gof
adduct
˝ = ´6.59 kcal/mol (R14a, HR1) is highly ineffective at T ˝ and above, but as Figure 3b shows, at
0.269 at T° + 40 compared to HR3b with a fraction of 0.119 remaining. This corresponds to
˝ ´ 20 (278.15 K) the system will have a CO -adduct fraction near 0.2. If we were to capture at T ˝ ´ 20
aT 21.5% increase in cycle load for the more 2exentropic reaction. Further, the fraction of CO2-adduct
and release
remaining for T˝ , the
atHR3c at system
the same will yield a relatively
temperature is 0.050.small
This is butanefficient cycle load.
8.1% increase over HR3bEven more
and a useful
31.4%
at low temperatures would be a reaction with ∆G ˝ = ´9 kcal/mol (R14h, HR2). The most important
increase over HR3a. As illustrated by the increase in cycle load percentage across each series, the
feature of
entropy this hypothetical
effects for the morereaction exergonic is its
HR3 variability
system are around
enhancedT˝ . The
by fraction
a factor ofof CO 2 -adduct
nearly 10 overcaptured
HR2.
of 0.492 at T ˝ and [CO ] = 400 ppm by this reaction is almost exactly between the two asymptotes.
2
After studying these hypothetical systems, it becomes pertinent to determine which would
Because the
provide of this,
bestitcapture
will vary andgreatly in capture
the capture with evenplays
temperature small andifferences
important in role.
temperature,
We haveasalready
can be
seen in Figure 3d. This great variability causes these reactions to
shown that ΔG° = −6.59 kcal/mol (R14a, HR1) is highly ineffective at T° and above, but as Figurebe useful for low temperatures while3b
they areatless ˝
T ´ 20
shows, T° −useful for higher
20 (278.15 K) thetemperatures.
system will have Considering
a CO2-adductR14h atfraction the0.2.
near fraction
If weof CO2to
were -adduct
capture is
greater than 0.9 at [CO ] = 400 ppm (Figure 3d). Raising the temperature to T ˝ + 20 yields the fraction
at T° − 20 and release at2 T°, the system will yield a relatively small but efficient cycle load. Even more
0.068 (Table
useful at low 1) temperatures
and an excellent cycle be
would load a fraction
reactionofwithoverΔG° 0.8. Even with a temperature
= −9 kcal/mol (R14h, HR2). variation from
The most
T ˝ (CO -adduct fraction = 0.492) to T˝ + 20, a cycle load fraction of 0.4 is obtained, a good collection
2
important feature of this hypothetical reaction is its variability around T°. The fraction of CO2-adduct
that requires
captured minimal
of 0.492 at T°heating.
and [CO2] = 400 ppm by this reaction is almost exactly between the two
at T ˝ + 20 (45 ˝ C), and release at T ˝ + 40, the cycle load
asymptotes. Because of this, it will avary
However when considering capture
greatly in capture with even small differences in temperature,
fraction
as can be will fall in
seen to 0.06,
Figure a very
3d. poor
This collection. Thus for
great variability higher
causes temperature
these reactionsclimates, a system
to be useful for with
low
a more robust exergonicity is desired, for example ∆G ˝ = ´11 kcal/mol (HR3). HR3b at T˝ + 20 has
temperatures while they are less useful for higher temperatures. Considering R14h at T° − 20 the
a CO2 capture
fraction fraction is
of CO2-adduct ofgreater
0.623, and thanincreasing
0.9 at [COthe temperature to T˝ + 40 (capture fraction of 0.119)
2] = 400 ppm (Figure 3d). Raising the temperature to
yields
T° + 20ayields
cycle load fraction 0.068
the fraction of 0.504, a decent
(Table 1) and collection.
an excellentEven better,
cycle loadforfraction
a capture of at T˝ (capture
over 0.8. Evenfraction
with a
of 0.966) with release at T ˝ + 40, the cycle load fraction is an excellent 0.847. At T ˝ reaction HR3 already
temperature variation from T° (CO2-adduct fraction = 0.492) to T° + 20, a cycle load fraction of 0.4 is
has a capture
obtained, a goodfraction of 0.966.
collection that Since
requires the minimal
system cannot
heating. load significantly more CO2 during capture,
thereHowever
is no benefitwhen considering a capture at T° + 20 (45a °C),
to using this system in a climate with temperature
and releasecooler
at T°than 25 ˝the
+ 40, C; in fact,load
cycle the
efficiency
fraction would
will fall tosuffer
0.06,because
a very poor morecollection.
heat would be required
Thus for higher to temperature
liberate the CO 2.
climates, a system with
a more robust exergonicity is desired, for example ΔG° = −11 kcal/mol (HR3). HR3b at T° + 20 has a
CO2 capture fraction of 0.623, and increasing the temperature to T° + 40 (capture fraction of 0.119)
yields a cycle load fraction of 0.504, a decent collection. Even better, for a capture at T° (capture
fraction of 0.966) with release at T° + 40, the cycle load fraction is an excellent 0.847. At T° reaction
HR3 already has a capture fraction of 0.966. Since the system cannot load significantly more CO2
during capture, there is no benefit to using this system in a climate with a temperature cooler than 25
C 2016, 2, 18 10 of 14

Our home state, Missouri, has great fluctuations in temperature through the seasons, so using a
C 2016, 2, 18 10 of 14
mixture of different capture systems may be most effective. In Columbia, Missouri, the average
temperature in December is 0.78 ˝ C which would indicate that a system with thermodynamic
temperature in December is 0.78 °C which would indicate that a system with thermodynamic
parameters similar to R14h would be best, while the average temperature in July is 25.4 ˝ C, indicating
parameters similar to R14h would be best, while the average temperature in July is 25.4 °C, indicating
that a reaction like HR3 would be considerably more effective [54]. For coastal or equatorial regions
that a reaction like HR3 would be considerably more effective [54]. For coastal or equatorial regions
with less variation in temperature, the use of one capture system would be more feasible.
with less variation in temperature, the use of one capture system would be more feasible.
The considerations emphasize the significance of the magnitude of the entropy of the capture
The considerations emphasize the significance of the magnitude of the entropy of the capture
reaction. The large magnitude of reaction entropy of the capture reaction is a direct consequence of
reaction. The large magnitude of reaction entropy of the capture reaction is a direct consequence of
the presence of two capture moieties in the active site of rubisco and we offer an analogy with the
the presence of two capture moieties in the active site of rubisco and we offer an analogy with the
illustration shown in Figure 8.
illustration shown in Figure 8.

Figure
Figure 8.8. The
The genius
genius of
of the
the rubisco-capture
rubisco-capture system
system stems
stems from
from the
the large
large reduction
reduction ofof system
system entropy
entropy
associated with bringing the two tethered capture moieties (the Mg 2+ site and the lysine amino group)
associated with bringing the two tethered capture moieties (the Mg site and the lysine amino group)
2+

together
together onon CO
CO22 capture. The principle
capture. The principle is
is well
well exemplified
exemplified by by the
the image
image of
of two
two leashed
leashed dogs
dogs biting
biting
on
on the same bone. In the absence of the bone, each dog enjoys great freedom in their accessible range
the same bone. In the absence of the bone, each dog enjoys great freedom in their accessible range
(illustration
(illustration on top).Biting
ontop). Bitingononthe
thesame bone
same curtails
bone the the
curtails accessible range
accessible and and
range the freedom of theof
the freedom dogs’
the
mobilities (bottom).
dogs’ mobilities (bottom).

3. Conclusions
3. Conclusions
In
In theoretical
theoretical studies
studies of
of chemical
chemical reactions
reactions with
with modern
modern methods
methods of of electronic
electronic structure
structure theory
theory
the
the reaction
reactionthermochemistry
thermochemistry is usually reported
is usually for thefor
reported stoichiometric reaction at
the stoichiometric standardatconditions
reaction standard
(1 atm, 25 ˝(1C)atm,
conditions and25the
°C)equilibrium
and the equilibrium Keq is related
constantconstant to the to
Keq is related reaction GibbsGibbs
the reaction free enthalpy via
free enthalpy
∆G ˝ = ∆H˝ ´ T ˝ ¨ ∆S˝ . We described the computation of the equilibrium concentrations of the
via ΔG° = ΔH° − T°·ΔS°. We described the computation of the equilibrium concentrations of the CO2-
adducts for the general capture reaction GCR and the rubisco-type capture reaction (RCR)
considering the atmospheric CO2 concentration via Henry’s law and as a function of temperature.
The equations were applied to the thermochemistry of rubisco-based small molecule model reactions
R1, R14a, and R14b, and three series of model reaction HR1–HR3 to illustrate the importance of the
C 2016, 2, 18 11 of 14

CO2 -adducts for the general capture reaction GCR and the rubisco-type capture reaction (RCR)
considering the atmospheric CO2 concentration via Henry’s law and as a function of temperature.
The equations were applied to the thermochemistry of rubisco-based small molecule model reactions
R1, R14a, and R14b, and three series of model reaction HR1–HR3 to illustrate the importance of the
Gibbs free enthalpy for the effective capture and of the reaction entropy for economic CO2 release at
elevated temperature. Having a favorable capture of free enthalpy is of course an absolute necessity,
but not all exergonic reactions are suitable CO2 capture systems. Successful CO2 capture systems must
allow for effective release as well, and this feature is controlled by the reaction entropy. It is hoped that
the presentation of the numerical examples provides useful guidelines for the design of more efficient
capture systems.
The active site of rubisco employs two capture moieties to trap the activator CO2 . The metal site is
attractive to any Lewis base, including water and CO2, and their exchanges will be fast. Eventually, a
CO2 molecule will occupy a ligand site of Mg2+ and it will then be trapped by Lewis-acid assisted
nucleophilic addition of the amino-group of lysine to the heterocumulene CO2 . This two-pronged
process allows for the capture of small amounts of CO2 in a huge excess of water, and the mechanism
has two major consequences for the thermochemistry. The endergonicity of the H2 O/CO2 replacement
is required to reduce the overall exergonicity of the CO2 capture reaction and to allow overall
reversibility. The second consequence for the RCR thermochemistry is the large reduction of system
entropy which is associated with bringing the two tethered capture moieties (the Mg2+ site and the
lysine NH2 group) together on CO2 capture. This entropy feature is crucial for the success of the
rubisco-based capture and release system. While chemists have a good sense of binding enthalpies, it
is usually more challenging to appreciate reaction entropies, and with this in mind we offer an analogy
in Figure 8. The principle of using a two-pronged capture system to ensure a large negative capture
entropy can be exemplified by two leashed dogs biting on the same bone. In the absence of the bone,
each dog has a large accessible range and they will enjoy the freedom to access much of their accessible
space (high mobility, high entropy). Biting on the same bone curtails the accessible range and reduces
the dogs’ mobilities (low entropy). This principle also is highlighted by the graphical abstract.

Acknowledgments: Acknowledgment is made to the donors of the American Chemical Society Petroleum
Research Fund for partial support of this research (#53415-ND4).
Author Contributions: Andrew Muelleman and Joseph Schell performed the research, computed the data, created
Figures 1–7, and contributed to the writing. Spencer Glazer created the art work in the graphical abstract and
Figure 8. Professor Rainer Glaser, Dipl.-Chem. guided the research and contributed to the writing.
Conflicts of Interest: The authors declare no conflict of interest.

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