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J. Chem. Thermodynamics
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a r t i c l e i n f o a b s t r a c t
Article history: Hydrolysis of cellulose to glucose is a key reaction in renewable energy from biomass and in mineraliza-
Received 4 April 2018 tion of soil organic matter to CO2. Conditional thermodynamic parameters, DhydG’, DhydH’, and DhydS’, and
Received in revised form 12 July 2018 equilibrium glucose concentrations are reported for the reaction C6H10O5(cellulose) + H2O(l) ¢
Accepted 7 August 2018
C6H12O6(aq) as functions of temperature from 0 to 100 °C. Activity coefficients of aqueous glucose solu-
Available online 16 August 2018
tion were determined as a function of temperature. The reaction free energy DhydG’ becomes more neg-
ative as temperature increases, suggesting that producing cellulosic biofuels at higher temperatures will
Keywords:
result in higher conversion. Also, cellulose is a major source of carbon in soil and is degraded by soil
Renewable energy
Biomass
microorganisms into CO2 and H2O. Therefore, global warming will make this reaction more rapid, leading
Soil organic matter to more CO2 and accelerated global warming by a positive feedback.
Lignocellulose Ó 2018 Elsevier Ltd.
Global warming
Glucose activity coefficient
https://doi.org/10.1016/j.jct.2018.08.006
0021-9614/Ó 2018 Elsevier Ltd.
M. Popovic et al. / J. Chem. Thermodynamics 128 (2019) 244–250 245
Table 1
DcrH°ref, DcrS°ref and DcrCp° values for Eqs. (5) and (6) were taken from reference 2. Heat capacity coefficients, qi, were obtained by fitting Eq. (9) to extrapolated heat capacity
values, see text around Eq. (8).
solutions, the results differ significantly. Some reports [7,8] give therefore, the reaction was divided into two reactions for which
solubility as mass of glucose per liter of solution, but reliable solu- thermodynamic data are available. One reaction is hydrolysis of
tion density data to convert these to temperature independent, and cellulose to crystalline glucose,
thus thermodynamically useful molal units, are not available.
Because reliable density data over the range of temperatures ana- ðC6 H10 O5 Þu ðH2 OÞ1 ðH2 OÞv ðsÞ
lyzed in this study are not available, only references that give sol- þ ðu v 1ÞH2 OðlÞ ¢uC6 H12 O6 ðcrÞ ð2Þ
ubility in mass fractions were used. Examination of experimental
procedures indicates the data published by Young [6] are the most where C6H12O6(cr) is anhydrous a-D-glucose. Even though a-D-
reliable and cover sufficient temperature range for this study, glucose monohydrate C6H12O6H2O is the most thermodynamically
Table 2. stable form up to 50 °C, reaction (2) was used in the entire temper-
Vapor pressure measurements of aqueous glucose solutions ature region where thermodynamic values were estimated. The
was reported by Taylor and Rowlinson [10]. These data were used product of reaction (1) is anhydrous a-D-glucose and the reactant
to calculate activity coefficients of aqueous glucose. in reaction (3) is anhydrous a-D-glucose. Therefore, even though
it is not the most thermodynamically stable form below 50 °C,
anhydrous a-D-glucose is used to complete the Hess’ law cycle in
2.1. Reactions Scheme 1. The other reaction is dissolution of crystalline glucose
to make the final aqueous solution.
The reaction of interest is cellulose hydrolysis in water to pro- C6 H12 O6 ðcrÞ ¢C6 H12 O6 ðaq; satÞ ð3Þ
duce an aqueous solution of glucose,
where C6H12O6 (aq, sat) is glucose in a saturated aqueous solution.
ðC6 H10 O5 Þu ðH2 OÞ1 ðH2 OÞv Completing the cycle also requires correction for the thermodynam-
ðsÞ
ics of dilution of glucose since the equilibrium concentrations differ,
þ ðu v 1ÞH2 OðlÞ ¢uC6 H12 O6 ðaq; hydÞ ð1Þ i.e. saturated and in equilibrium with cellulose.
(C6H10O5)u∙(H2O)1∙(H2O)v (s) is cellulose, u is the average
C6 H12 O6 ðaq; satÞ ¢C6 H12 O6 ðaq; hydÞ ð4Þ
number of monosaccharide units in the polymer, v is the average
number of waters of hydration [2], C6H12O6(aq, hyd) is glucose in Scheme 1 shows how the thermodynamic data for reactions (2),
the cellulose hydrolysis equilibrium solution. No direct thermody- 3 and 4 are combined to determine the thermodynamics of
namic measurements have been made on this reaction, and reaction (1).
Table 2
Solubility of anhydrous a-D-glucose(cr) in water obtained from w values in Table 1 in reference 6. Molality is denoted b and mass fraction is denoted w. Conversion between b and
w is done with the equation b = w/[180.16 (1-w)], where 180.16 is the molar mass of glucose. Conditional equilibrium constants (K’sol) and conditional Gibbs energy changes
(DsolG’) were calculated from solubilities for dissolution of anhydrous a-D-glucose in water.
Scheme 1. Separating the cellulose hydrolysis to aqueous glucose reaction into components.
246 M. Popovic et al. / J. Chem. Thermodynamics 128 (2019) 244–250
2.2. Cellulose hydrolysis to solid glucose ^ ref þ 1 q T 3 T 3 þ 1 q T 2 T 2
^ ¼ Dcr SA
Dcr SA 3 ref 2 ref
3 2
The thermodynamics of reaction (2) can be extrapolated from T
þ q1 T T ref þ q0 ln ð11Þ
25 to 100 °C by assuming DcrCp° does not change with temperature T ref
and using the value of DcrCp° (Table 1) from Goldberg et al. [2] as a
R R Substituting Eqs. (10) and (11) into (7), and comparing DcrG°
constant in integrating dH = CpdT and dS = (Cp/T)dT, i.e.,
values found from DcrCp° described by Eq. (8) and found from con-
^ ref þ Dcr C p T T ref
Dcr H ¼ Dcr HA ð5Þ stant DcrCp°, indicates the approximation in the latter method
causes an average error of 0.16% and a maximum error of 1.12%
^ ¼ Dcr SA
Dcr SA ^ ln T=T ref
^ ref þ Dcr C p A ð6Þ compared with Eq. (8), thus justifying the use of Eqs. (5) and (6)
in subsequent derivations.
DcrH°ref and DcrS°ref are the standard reaction enthalpy and
entropy at the reference temperature 25 °C, taken from Goldberg 2.3. Glucose solution
et al. [2] (Table 1).
The standard Gibbs energy change of reaction (2), DcrG°, was The thermodynamic parameters for reaction (3), solution of
then calculated with the equation crystalline glucose into water, are based on the solubility of anhy-
^ ¼ Dcr HA
^ þ T Dcr SA
^ drous a-D-glucose in water, Table 2. For practical purposes, con-
Dcr GA ð7Þ
centrations are more convenient than activities, so conditional
To test whether assuming constant DcrCp° leads to a significant thermodynamic parameters of dissolution of glucose in water
error in the final results, the heat capacity data for cellulose [2] and based on molality were determined. The conditional equilibrium
anhydrous a-D-glucose [3] were fit to constant for reaction (3) is
eq
C p ðT Þ ¼ p1 DðHD Þ þ p2 DðHE Þ þ p3 T þ p4 T 2 ð8Þ K 0 sol ¼ bsol ð12Þ
and extrapolated to 100 °C. Cp(T) is the heat capacity as a function of where beq sol is the equilibrium solubility of glucose expressed in
temperature, D(HD) is the Debye function, HD is the Debye temper- molal units. The conditional equilibrium constants of reaction (3)
ature, E(HE) is the Einstein function, HE is the Einstein temperature, are given in Table 2. (Note that a prime symbol refers to a saturated
T is Kelvin temperature, and p1, p2, p3 and p4 are coefficients that glucose solution as a specified condition.)
satisfy p1 + p2 + p3 + p4 = 1. The fitted parameters are given in The conditional enthalpy of dissolution of glucose in water,
Table 3. The data were then corrected for cellulose water content DsolH’, is determined with the van’t Hoff relation
and crystallinity and averaged as described by Goldberg et al. [2] 0 0
Dsol H dlnK sol
The extrapolated Cp data were then used to find DcrCp°, which ¼ ð13Þ
was then used to extrapolate the DcrG⁰, DcrH⁰, and DcrS⁰ of reaction R dð1=T Þ
(2) up to 100 °C. Because the results did not differ significantly from The van’t Hoff plot is shown in Fig. 1 with data from Table 2
the approximation of constant DcrCp°, Eqs. (5) and (6) are used in all fitted to a second order polynomial in T1.
subsequent calculations.
Using the extrapolated heat capacities of cellulose and anhy- ln K 0 sol ¼ mT 2 þ nT 1 þ k ð14Þ
drous a-D-glucose and the water heat capacity determined by m, n and k are constants given in Table 4. The first derivative of
Osborne et al. [4], the heat capacity change, DcrCp°, for reaction the polynomial gives the enthalpy change for dissolution as
(2) was determined for each of the cellulose allomorphs and fit
0
to a third order polynomial in T where T is temperature in Kelvins. Dsol H ¼ R 2mT 1 þ n ð15Þ
2 3
Dcr C p ðT Þ ¼ q0 þ q1 T þ q2 T þ q3 T ð9Þ Values of DsolH’ are given in Table 5.
The values of q0, q1, q2, and q3 are given in Table 1. The conditional Gibbs energy change for dissolution of glucose
DcrCp (T) for reaction (2) was extrapolated to 100 °C and substi- in water, DsolG’, is related to the conditional equilibrium constant
R R by
tuted into the equations dH = CpdT and dS = (Cp/T)dT, which were
then integrated from 25 °C to 100 °C. 0
Dsol G ¼ RT ln K 0 sol ð16Þ
Dcr HA ^ ref þ 1 q T 4 T 4 þ 1 q T 3 T 3
^ ¼ Dcr HA The values of DsolG’ given in Table 4 were then fitted to the
4 3 ref
3 2 ref
function,
1
þ q1 T 2 T 2ref þ q0 T T ref ð10Þ 0 1 1
2 Dsol G ¼ DHI DaT ln ðT Þ DbT 2 DcT 1 þ IT ð17Þ
2 2
Table 3
Coefficients for Eq. (8) obtained by fitting heat capacity data for cellulose from reference 2 and for anhydrous a-D-glucose(cr) from reference 3.
Fig. 1. Van‘t Hoff plot for dissolution of crystalline a-D-glucose in water, Fig. 2. Comparison of DsolS’ found by method 1 -the Gibbs equation (Eq. (18)), and 2
C6H12O6(cr) ¢ C6H12O6(aq). The line going through the points is a second order – first derivative of the Gibbs energy (Eq. (19)).
polynomial fit.
273.15 8.1803 45.4652 4.2383 Ddil G ¼ Dmix Geq Dmix Gsat ð20Þ
278.15 8.9192 48.2123 4.4908
283.15 9.6320 50.7924 4.7496 The free energy of mixing is a function of composition and
288.15 10.3201 53.2189 5.0147 temperature and is given by the equation
293.15 10.9847 55.5040 5.2861
298.15 11.6270 57.6589 5.5637 Dmix Geq ¼ nRT ðxw ln xw þ xGlc ln xGlc þ xw ln cw þ xGlc ln cGlc Þ ð21Þ
303.15 12.2481 59.6934 5.8477
308.15 12.8490 61.6170 6.1379 xw and xGlc are the mole fractions of water and glucose, respec-
313.15 13.4308 63.4379 6.4345 tively; n is the total number of moles in the solution, while cw and
318.15 13.9943 65.1639 6.7373 cGlc are the activity coefficients of water and glucose, respectively
323.15 14.5403 66.8020 7.0464
[12].
328.15 15.0697 68.3586 7.3618
333.15 15.5832 69.8396 7.6835
The activity coefficients were found from vapor pressure
338.15 16.0816 71.2505 8.0114 measurements done by Taylor and Rowlinson [10], using Raoult’s
343.15 16.5654 72.5964 8.3457 law
348.15 17.0353 73.8817 8.6863
p
353.15 17.4919 75.1107 9.0331 cw ¼ ð22Þ
358.15 17.9357 76.2874 9.3862 ð1 xGlc Þp
363.15 18.3674 77.4153 9.7456
368.15 18.7873 78.4979 10.1113 where p is the vapor pressure of the glucose solution of concentra-
373.15 19.1959 79.5381 10.4833 tion xGlc, and p* is the vapor pressure of pure water at the same tem-
perature [12,13].
Since the experimental data did not cover the entire range of
DsolG’ is in J/mol, T is in K, and DHI, Da, Db, Dc and I are con- concentrations and temperatures, it was fitted to the Margules
stants given in Table 4. Function (17) was chosen because it is equation and then extrapolated. The Margules equation gives the
the most physically meaningful function for fitting free energy activity coefficient of the solvent as a function of the solute
248 M. Popovic et al. / J. Chem. Thermodynamics 128 (2019) 244–250
concentration and temperature [12,13,15]. It was found that the where wGlc,sat is the solubility of glucose in water in mass fraction
best fit of the data, with the least number of parameters is given percent and t is temperature in degrees Celsius. The mole fraction
by a two-suffix Margules equation of glucose was calculated using the equation
xGlc,sat = (wGlc/MGlc)/{(wGlc/MGlc) + [(1 – wGlc)/Mw]}, where MGlc
ln cw ¼ a2 x2Glc þ a3 x3Glc ð23aÞ
and Mw are molar masses of glucose and water, respectively. How-
a2 and a3 are temperature-dependent coefficients ever, there is a problem with the final concentration xGlc,hyd:
a2;0 according to Eqs. (20) and (21), DdilG depends on the composition
a2 ¼ þ a2;1 ð23bÞ of the hydrolysis mixture, that is, it depends on the equilibrium
h
glucose mole fraction xGlc,hyd, related to beq hyd by the equation
a3;0 xGlc,hyd = 1/{1 + [1/(Mw beq hyd)]}. On the other hand, according to
a3 ¼ þ a3;1 ð23cÞ Eqs. (35) and (36), beq
h hyd depends on DdilG. So, we have a circular
problem, finding beq hyd requires DdilG, while to find DdilG we need
where h = T/298.15 K, while a2,0; a2,1; a3,0; and a3,1 are the fitting
beq
hyd. The problem was solved iteratively. Starting from a guess
parameters, given in Table 5. The fitting was done using least-
value of DdilG, DdilG and beq hyd were iteratively calculated until
squares regression. The sum of the squares of the residuals was
convergence was reached. The calculation was done by giving an
minimized using the GRG-Nonlinear method in Excel Solver, as
initial DdilG, then calculating beq hyd and from it a new DdilG, until
described by Chapra and Canale [14]. The absolute average devia-
the old and the new values of DdilG became nearly identical, using
tion of the fit was 11.7%.
GRG-Nonlinear method in Excel Solver. The DdilG values
The activity coefficient of glucose can be found using the Gibbs-
determined in this way are given in Table 6.
Duhem Eq. [12,13] and is a function of temperature and the mole
Enthalpy DdilH and entropy DdilS change of reaction (4) were
fraction of water.
calculated by fitting a polynomial to DdilG as a function of temper-
ln cGlc ¼ b2 x2w þ b3 x3w ð24aÞ ature. The first derivative was used to determine the entropy
change: DdilS = d(DdilG)/dT. The enthalpy change was calculated
b2 and b3 are temperature-dependent coefficients, that are
from the Gibbs equation: DdilH = DdilG + T DdilS. The values of DdilH
related to a2 and a3:
and DdilS are given in Table 6. Like with DdilG, each cellulose
3 allomorph has its own value, because the equilibrium glucose
b2 ¼ a2 þ a3 ð24bÞ
2 concentrations differ and thus the dilution thermodynamic
parameters are different as well.
b3 ¼ a3 ð24cÞ
A review of the theory behind the Margules equation is given by 2.5. Cellulose hydrolysis to aqueous glucose
Sandler [15], while Starzak and Mathlouthi [13] give a detailed
explanation of how it is applied in practice. The conditional Gibbs energy change for hydrolysis of cellulose
Using Eqs. (20), (21), (23) and (24), DdilG can be determined, to aqueous glucose (reaction (1)), DhydG’, is found by adding the
knowing the initial and final concentration of the solution xGlc,sat Gibbs energy changes for reactions (2), (3) and (4):
and xGlc,hyd, respectively. The initial concentration xGlc,sat is the sol- 0
^ þ Dsol G þ Ddil G
Dhyd G ¼ Dcr GA
0
ð26Þ
ubility of glucose in water, which was found using an equation
given by Young [6]. The values of DhydH’, DhydS’ and DhydG’ are given in Table 7. After
4 2
substituting Eq. (17) for DsolG’ and Eqs. (5), (6), and (7) for DcrG° and
wGlc;sat ¼ 53:8 þ 0:335t þ 3:65 10 t ð25Þ grouping the terms by the power of T, the final result for DhydG’ is
Table 6
Thermodynamic parameters of reaction (4), C6H12O6 (aq,sat) ¢ C6H12O6 (aq,hyd) obtained as explained in the text following Eq. (25).
Table 7
Conditional thermodynamic parameters for hydrolysis of cellulose into aqueous glucose – reaction (1), (C6H10O5)u∙(H2O)1∙(H2O)v (s) + (u-v-1)H2O(l) ¢ uC6H12O6 (aq, hyd), obtained
from Eqs. (26), (28), and (29) using data from Tables 4, 5 and 6 with data from Table 1.
n o
0 1
Dhyd G ¼ DbT 2 þ Dcr C p A^ 1 þ ln T ref þ I Dcr SA
^ ref T the approximation leads to an average error less than 0.15%, the
2 highest error observed was less than 2.65%.
1 Mass fraction conversions of cellulose into glucose were calcu-
DcT 1 Dcr C p A ^ þ Da T ln ðT Þ
2 lated from the beq hyd values. For the hydrolysis reaction per
þ Dcr HA ^ T ref þ Ddil G
^ ref þ DHI Dcr C p A ð27Þ
monomer,
eq The uncertainties db are in the form beq hyd ± db and are given as a function of tem-
K 0 hyd ¼ bhyd ð36Þ perature by the following equations.
Amorphous cellulose: db = 1.279∙10 T 3 –1.146∙102 T 2 + 3.454 T – 345.8.
5
Conflicts of interest
Acknowledgements
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bioethanol or other fuels and chemicals that can be derived from JCT 2018-168