Appendices
Appendix - I
Calculation for Catalyst Preparation
(A) Synthesis of LaCoO3 perovskite catalyst by citrate complexation method
Atomic weight of lanthanum (La): 138.91 ~ 139 g/mol
Atomic weight of cobalt (Co): 58.93 ~ 59 g/mol
Molecular weight of LaCoO3 = 139 + 59 + (3 x 16)
= 246 g/mol
Molecular weight of lanthanum nitrate [La(NO3)3Â+2O]
= 139 + (3 x 14) + (9 × 16) + (6 x 2) + (6 × 16)
= 433 g/mol
Molecular weight of cobalt nitrate [Co(NO3)2Â+2O]:
= 58.93 + (2 x 14) + (6 × 16) + (6 x 2) + (6 × 16 )
= 290.93 g/mol ~ 291 g/mol
Preparation of LaCoO3 perovskite catalyst: 10 g
Calculation of lanthanum (La) and lanthanum nitrate [La(NO3)3Â+2O] :
246 g LaCoO3
=
139 g lanthanum (La)
10 g LaCoO3
=
?
=
10 × 139
246
=
5.65 g lanthanum (La)
139 g lanthanum (La)
=
433 g lanthanum nitrate [La(NO3)Â6H2O]
5.65 g lanthanum (La)
=
?
=
5.65 × 433
139
=
17.60 g lanthanum nitrate [La(NO3)3Â+2O]
Calculation of cobalt (Co) and cobalt nitrate [Co(NO3)2Â+2O] :
246 g LaCoO3
=
59 g cobalt (Co)
10 g LaCoO3
=
?
=
10 × 59
246
=
2.398 g cobalt (Co)
59 g cobalt (Co)
=
291 g cobalt nitrate [Co(NO3)2Â+2O]
2.398 g cobalt (Co)
=
?
=
2.398 × 291
59
=
11.82 g cobalt nitrate [Co(NO3)2Â+2O]
Calculation of citric acid:
Molecule weight of CA (C6H8O7) : 192.13 g/mol
§ Moles of citric acid ·
¨
¸
© Moles of metal cations ¹
=
Amount of citric acid
10 % excess amount of citric acid
1
=
ª 5.65 2.398 º
«¬ 139 59 »¼
=
0.0812 mol = 0.0812 × 192.13 = 15.60 g
=
17.16 g citric acid
(B) Synthesis of La0.8Sr0.2Co0.8Cu0.2O3 perovskite catalyst by citrate complexation
method
Atomic weight of lanthanum (La): 138.91 ~ 139 g/mol
Atomic weight of cobalt (Co): 58.93 ~ 59 g/mol
Atomic weight of strontium (Sr): 87.62 g/mol
Atomic weight of copper (Cu): 63.55 g/mol
Molecular weight of La0.8Sr0.2Co0.8Cu0.2O3:
= [0.8 × 139] + [0.2 × 87.62] + [0.8 × 59] + [0.2 × 63.55] + [3 × 16]
= 236. 63 g/mol
Molecular weight of lanthanum nitrate [La(NO3)3Â+2O] :
= 138.91 + (3 × 14) + (9 × 16) + (6 × 2) + (6 × 16) = 432.91 g/ mol
~ 433 g/mol
Molecular weight of strontium nitrate [Sr(NO3)2]:
= 87.62 + (2 × 14) + (6 × 16)
= 211.62 g/mol
Molecular weight of cobalt nitrate [Co(NO3)2Â+2O]:
= 58.93 + (2 × 14) + (6 × 16) + (6 × 2) + (6 × 16 ) = 290.93 g/mol
~291 g/mol
Molecular weight of copper nitrate [Cu(NO3)2Â+2O]:
= 63.55 + (2 × 14) + (6 × 16) + (3 × 2) + (16 × 3)
= 241.55 g/mol
Preparation of La0.8Sr0.2Co0.8Cu0.2O3 perovskite catalyst: 10 g
Calculation of lanthanum (La) and lanthanum nitrate [La(NO3)3Â+2O] :
236.63 g La0.8Sr0.2Co0.8Cu0.2O3
(0.8 × 139) g lanthanum (La)
=
?
=
10 × 0.8 × 139
236.63
=
4.70 g lanthanum (La)
139 g lanthanum (La)
=
433 g lanthanum nitrate [La(NO3)3Â+2O]
4.70 g lanthanum (La)
=
10 g
La0.8Sr0.2Co0.8Cu0.2O3
=
?
=
4.70 × 433
139
=
14.64 g lanthanum nitrate [La(NO3)3Â+2O]
Calculation of strontium (Sr) and stromtium nitrate [Sr(NO3)2]
236.63 g La0.8Sr0.2Co0.8Cu0.2O3
(0.2 × 87.62) g strontium (Sr)
=
?
=
10 x 0.2 x 87.62
236.63
=
0.74 g strontium (Sr)
87.62 g strontium (Sr)
=
211.62 g strontium nitrate [Sr(NO3)2]
0.74 g strontium (Sr)
=
10 g
La0.8Sr0.2Co0.8Cu0.2O3
=
?
=
0.74 ×211.62
87.62
=
1.79 g strontium nitrate [Sr(NO3)2]
Calculation of cobalt (Co) and cobalt nitrate [Co(NO3)2.6H2O] :
236.63 g La0.8Sr0.2Co0.8Cu0.2O3
10 g
La0.8Sr0.2Co0.8Cu0.2O3
=
=
(59 × 0.8) g cobalt (Co)
?
=
10 × 59 × 0.8
236.63
=
1.99 g cobalt (Co)
59 g cobalt (Co)
=
291 g cobalt nitrate [Co(NO3)2Â+2O]
1.99 g cobalt (Co)
=
?
=
1.99 × 291
59
=
9.83 g cobalt nitrate [Co(NO3)2Â+2O]
Calculation of copper (Cu) and copper nitrate [Cu(NO3)2.3H2O] :
236.63 g La0.8Sr0.2Co0.8Cu0.2O3
10 g
La0.8Sr0.2Co0.8Cu0.2O3
=
(63.55 ×0.2) g copper (Cu)
=
?
=
10 × 63.55 × 0.2
236.63
=
0.537 g copper (Cu)
63.546 g copper (Cu)
=
0.537 g copper (Cu)
=
241.55 g copper nitrate [Cu(NO3)2Â+2O]
?
=
0.8055×241.55
63.55
=
2.04 g copper nitrate [Cu(NO3)2Â+2O]
Calculation of citric acid:
Molecule weight: 192.13 g/mol
§ Moles of citric acid ·
¨
¸ =
© Moles of metal cations ¹
Amount of citric acid
1.5
0.54 ·
§ 4.70 0.74 1.99
¸
© 139 87.62 59 63.546 ¹
=
1.5 × ¨
=
1.5 × 0.0844 = 0.1266 mol = 0.1266 × 192.13 g = 24.38 g
10 % excess amount of citric acid = 26.81 g Citric acid
(C) Synthesis of LaCoO3 perovskite catalyst by co-precipitation method
Atomic weight of lanthanum (La): 138.91 ~ 139 g/mol
Atomic weight of cobalt (Co): 58.93 ~ 59 g/mol
Molecular weight of LaCoO3 = 139 + 59 + (3 x 16)
= 246 g/mol
Molecular weight of lanthanum nitrate [La(NO3)3Â+2O]
= 139 + (3 x 14) + (9 × 16) + (6 x 2) + (6 × 16) = 433 g/mol
Molecular weight of cobalt nitrate [Co(NO3)2Â+2O]:
= 58.93 + (2 × 14) + (6 × 16) + (6 × 2) + (6 × 16 )
= 290.93 g/mol ~ 291 g/mol
Preparation of LaCoO3 perovskite catalyst: 10 g
Calculation of lanthanum (La) and lanthanum nitrate [La(NO3)3Â+2O] :
246 g LaCoO3
=
139 g lanthanum (La)
10 g LaCoO3
=
?
=
10 × 139
246
=
5.65 g lanthanum (La)
139 g lanthanum (La)
=
433 g lanthanum nitrate [La(NO3)3Â+2O]
5.65 g lanthanum (La)
=
?
=
5.65 × 433
139
=
17.60 g lanthanum nitrate [La(NO3)3Â+2O]
Calculation of cobalt (Co) and cobalt nitrate [Co(NO3)2Â+2O] :
246 g LaCoO3
=
59 g cobalt (Co)
10 g LaCoO3
=
?
=
10 × 59
246
=
2.398 g cobalt (Co)
59 g cobalt (Co)
=
291 g cobalt nitrate [Co(NO3)2Â+2O]
2.398 g cobalt (Co)
=
?
=
2.398 × 291
59
=
11.82 g cobalt nitrate [Co(NO3)2Â+2O]
Calculation of 1M Na2CO3 solution
M
=
Moles of Na 2 CO 3
Volume of solution (lt)
=
§ Moles of Na 2 CO 3 ·
¨
¸
© 500 ml 0.5 lt ¹
Moles of Na2CO3
=
0.5 mol
Weight of Na2CO3
=
0.5 mol × molecular wt of Na2CO3
=
0.5 mol × 105.98 g/mol
=
52.99 g ~ 53.00 g of Na2CO3 (1 M in 500 ml)
(D) Synthesis of LaCoO3 perovskite catalyst by reactive grinding method
Atomic weight of lanthanum: 139 g/mol
Atomic weight of cobalt: 59 g/mol
Molecular weight of LaCoO3: 139 + 59 + (3 × 16) = 246 g/mol
Molecular weight of La2O3: (2 × 139) + (3 × 16) = 326 g/mol
Molecular weight of Co3O4: (3 × 59) + (4 × 16) = 241 g/mol
Preparation of LaCoO3 perovskite catalyst: 15 g
Calculation of lanthanum (La) and lanthanum oxide (La2O3)
246 g of LaCoO3
=
15 g LaCoO3
=
139 g lanthanum (La)
?
=
139 × 15
246
=
8.476 g of lanthanum (La)
Similarly,
(2 × 139) g lanthanum (La) =
8.476 g lanthanum (La)
326 g La2O3
= ?
= 8.476 × 326
2 × 139
= 9.939 g of La2O3
#
10 g La2O3
Calculation of cobalt (Co) and cobalt oxide (Co3O4)
246 g LaCoO3
= 59 g cobalt (Co)
15 g LaCoO3
= ?
= 59 × 15
246
= 3.598 g of cobalt
Similarly,
(3 × 59) g cobalt (Co)
= 241 g Co3O4
3.598 g of cobalt (Co)
=
?
= 3.598 × 24
3 × 59
= 4.899 g of Co3O4
#
5 g of Co3O4
Appendix - II
Gas Chromatography Analysis
&
Carbon balance
Weight versus area using calibration mixture for calculation of calibration factor
Gas
Retention time
(RT)
3.620
3.667
3.695
4.707
4.693
4.715
25.530
25.746
25.879
N2
CO
CO2
Area
8183298.2
6174418.6
4269818.8
8056620
5447340
3499280
8668036
754347.2
5732034.5
Syringe volume
(µl)
2000
1500
1000
2000
1500
1000
2000
1500
1000
Weight
(g)
2.2904 × 10-3
1.71864 × 10-3
1.145844 × 10-3
2.2904 × 10-3
1.71864 × 10-3
1.145844 × 10-3
3.599 × 10-3
2.700 × 10-3
1.80 × 10-3
Calculation: PV = nRT for N2 (Atomic weight of N2 = 28)
nN2 = PV/RT
= 1 atm × 2000 × 10-6 (l) / 0.082 (l atm/mol K) × 298 K
= 8.18 × 10-5 mol
Mass of N2 = n × molecular weight
Mass of N2 = 8.18 × 10-5 × 28 g
= 2.2904 × 10-3 g
Calibration factor of product gases on Shin Carbon micro packed column using µTCD
CFi (calibration factor) = (weight/area)i / (weight/area)N2, where i = CO2, N2, CO
CFCO (calibration factor) = (weight/area)CO / (weight/area)N2 = 4×10-10/5×10-10 = 0.8
Compound
CO2
N2
CO
Calibration factor
1.2
1
0.8
0.004
0.0035
Carbon dioxide
Weight (g)
0.003
0.0025
0.002
0.0015
0.001
0.0005
0
0
2000000
4000000
6000000
8000000
10000000
8000000
10000000
Area (µV)
0.0035
0.003
Nitrogen
Weight (g)
0.0025
0.002
0.0015
0.001
0.0005
0
0
2000000
4000000
6000000
Area (µV)
0.0035
0.003
Weight (g)
0.0025
Carbon monoxide
0.002
0.0015
0.001
0.0005
0
0
2000000
4000000
6000000
8000000
10000000
Area (µV)
Calibration for product distribution and conversion using calibration factor:
LaCo0.95Pd0.05O3 perovskite catalyst prepared by co-precipitation method, calcined at 800 0C
for 5 h and CO oxidation activity was carried using simulated gas mixture of 1% CO, 1% O2
and balance N2.
Total flow rate 400 ml/min
Inlet flow rates:
Carbon monoxide = 4 ml/min
= 0.28 × 10-3 kg/h
Oxygen
= 4 ml/min
= 0.314 × 10-3 kg/h
Nitrogen
= 392 ml/min = 26.94 × 10-3 kg/h
Outlet flow rates:
Carbon monoxide = CFCO × (area of CO) × (weight / area)N2
= 0.8 × 0 × (2.2904 × 10-6/8266164.3) = 0 kg/h
Carbon dioxide = CFCO2 × (area of CO2) × (weight/area)N2
= 1.2 × 77978.1 × (2.2904 × 10-6/8266164.3)
= 2.59 × 10-8 kg in 2000 µl = 0.29 × 10-3 kg/h
Nitrogen = CFN2 × (area of N2) × (weight / area)N2 = 0.026 kg/h
Carbon balance (%) = 100 x {[CO]out +[CO2]out}/{[CO]in = 100 x 0.29 × 10-3/ 0.28 × 10-3 =
103 %
The mass balance with respect to carbon was 100 ± 3%.
Appendix ± III
XRD patterns
Compound: LaCoO3
JCPDS card No: 00-025-1060
Crystal system: Rhombohedral
Space group: R-3m
Compound: LaCoO3
JCPDS card No: 00-009-0358
Crystal system: Rhombohedral
Space group: R-3m
Compound: LaCoO3
JCPDS card No: 00-006-0491
Crystal system: Unknown
Space group: -
OR
Compound: LaCoO3
JCPDS card No: 00-048-0123
Crystal system: Trigonal
Space group: R-3c(167)
Compound: LaMnO3.15
JCPDS card No: 00-032-0484
Crystal system: Hexagonal
Space group: -
Compound: La0.96MnO3.15
JCPDS card No: 00-089-0678
Crystal system: Trigonal
Space group: R-3c(167)
Compound: LaFeO3
JCPDS card No: 00-037-1493
Crystal system: Orthorhombic
Space group: Pn*a
Compound: LaFeO3
JCPDS card No: 00-075-0439
Crystal system: Cubic
Space group: Pm-3m(221)
Perovskite structure
RG 29
RG 27
RG 23
X-ray diffraction patterns of the LaCoO3 perovskite catalysts prepared by reactive
grinding method. Conditions: J 350, S 200, BP 15, milling time = 5, 11 and 15 h, heat
treatment at 600 0C for 5 h
Perovskite structure
RG 25
RG 22
X-ray diffraction patterns of the LaCoO3 perovskite catalysts prepared by reactive
grinding method. Conditions: J 350, S 200, BP 15, milling time = 5 and 11 h, without
heat treatment
Perovskite structure
RG 27
RG 23
X-ray diffraction patterns of the LaCoO3 perovskite catalysts prepared by reactive
grinding method. Conditions: J 350, S 200, BP 15, milling time = 5 and 11 h, heat
treatment at 600 0C for 5 h
Appendix ± IV
N2 adsorption-desorption isotherms
70
Volume adsorbed cm3\g (STP)
60
50
40
30
20
10
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Relative Pressure (P/P0)
N2 adsorption-desorption isotherm of CT 10 perovskite catalyst
(LaMnO3 perovskite catalyst prepared by citrate method, calcined at 600 0C for 5 h)
90
Volume adsorbed cm3\g (STP)
80
70
60
50
40
30
20
10
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Relative Pressure (P/P0)
N2 adsorption-desorption isotherm of CT 12 perovskite catalyst
(LaFeO3 perovskite catalyst prepared by citrate method, calcined at 800 0C for 5 h)
Volume adsorbed cm3\g (STP)
25
20
15
10
5
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Relative Pressure (P/P0)
N2 adsorption-desorption isotherm of CT 9 perovskite catalyst
(LaCo0.95Pd0.05O3 perovskite catalyst prepared by citrate method, calcined at 800 0C for
5 h)
Volume adsorbed cm3\g (STP)
25
20
15
10
5
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Relative Pressure (P/P0)
N2 adsorption-desorption isotherm of COP 6 perovskite catalyst
(LaCo0.95Pd0.05O3 perovskite catalyst prepared by co-precipitation method, calcined at
750 0C for 5 h)
35
Volume adsorbed cm3\g (STP)
30
25
20
15
10
5
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Relative Pressure (P/P0)
N2 adsorption-desorption isotherm of RG 46 perovskite catalyst
(La0.8Sr0.2Co0.8Cu0.2O3 perovskite catalyst prepared by reactive grinding method.
Conditions: J 350, S 200, BP 15, milling time 11 h, heat treatment at 600 0C for 5 h)
Volume adsorbed cm3\g (STP)
30
25
20
15
10
5
0
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
Relative Pressure (P/P0)
N2 adsorption-desorption isotherm of RG 50 perovskite catalyst
(La0.8Ce0.2CoO3 perovskite catalyst prepared by reactive grinding method. Conditions: J
350, S 200, BP 15, milling time = 11 h, without heat treatment)
Appendix ± V
SEM and TEM micrographs
SEM micrograph of CT 3 perovskite catalyst
(LaCoO3 perovskite catalyst prepared by citrate method, calcined at 800 0C for 5 h)
SEM micrograph of CT 11 perovskite catalyst
(LaMnO3 perovskite catalyst prepared by citrate method, calcined at 800 0C for 5 h)
SEM micrograph of CT 13 perovskite catalyst
(LaFeO3 perovskite catalyst prepared by citrate method, calcined at 800 0C for 5 h)
SEM micrograph of CT 8 perovskite catalyst
(LaCo0.95Pd0.05O3 perovskite catalyst prepared by citrate method, calcined at 800 0C for
5 h)
SEM micrograph of COP 7 perovskite catalyst
(LaMnO3 perovskite catalyst prepared by co-precipitation method, calcined at 750 0C
for 5 h)
SEM micrograph of COP 8 perovskite catalyst
(LaFeO3 perovskite catalyst prepared by co-precipitation method, calcined at 750 0C for
5 h)
SEM micrograph of COP 6 perovskite catalyst
(LaCo0.95Pd0.05O3 perovskite catalyst prepared by co-precipitation method, calcined at
750 0C for 5 h)
SEM micrograph of RG 5 perovskite catalyst
(LaCoO3 perovskite catalyst prepared by reactive grinding method. Conditions: J 350, S
200, BP 15, milling time = 22 h, heat treatment at 600 0C for 5 h)
TEM photogrpah of CT 2 perovskite catalyst
(LaCoO3 perovskite catalyst prepared by citrate method, calcined at 750 0C for 5 h)
Appendix ± VI
Mechanism over LaB1-xB'xO3 (B = Co, Mn,
Fe; B'= Cu, Pd) perovskite catalysts
for CO oxidation
It is reported in the literature (Royer et al., 2005b; Zhang et al., 2006a, 2006d; Levasseur and
Kaliaguine, 2008) that the non-stoichiometric oxygen of provskites plays an important role in
redox reactions. O2-TPD experiments show that there are two types of oxygen released from
the perovskites structure: the one coming from the surface (Į-O2) and the other from the bulk
(ȕ-O2). The following mechanism is proposed over LaMO3 (M = Co, Mn, Fe) perovskites for
redox reaction.
In mechanism, the first step occurs during calcination under air in which anion vacancies
generate due to condensation of the surface hydroxyl groups followed by the addition of
gaseous oxygen.
H O
2
M n OH M n OH 
o M (n 1) V0 M n O (1)
The interaction of molecular oxygen with the site having an excess of electronic charge to
form adsorbed oxygen (O2í) i.e. instantaneous formation of Į-O2 by adsorbing O2 at anion
vacancy
2
M (n 1) V0 Oo
M n O 2 (2)
Where n = 4 or 3 and V0 is an anion vacancy.
The following two reactions are proposed for the desorption of Į-O2 from the surface.
O
M n O M n O 2 2 o M n O 2 M n O 2
(3)
M n O 2 
o M (n 1) V0 O 2
(4)
The presence of a neighbor site Mn+O- as illustrated in equation (3) interact with the adsorbed
oxygen species which weaken the interaction between the adsorbed oxygen and the low
coordination M site and to facilitate the O2 desorption process. Therefore, equation (3) is
DVFULEHG WR Į1-O2 GHVRUSWLRQ ZKLOH WKH Į2-O2 desorption occurring at higher temperature
associated with the reduction of Mn+ into M(n-1)+ (n = 3 or 4) is then described by equation (4).
The ȕ-O2 desorbed above 600 0C is defined as the oxygen liberated from the lattice leaving
oxygen bulk vacancies and reduced cations. Due to the number of monolayers desorbed at
KLJKHUWHPSHUDWXUHEHLQJKLJKHUWKDQLWLVSRLQWHGRXWWKDWȕ-O2 is originating from the bulk.
Hence, the amount of ȕ-O2 desorbed is thus generally considered as a measure of lattice
oxygen mobility. It is suggested that first step consists in the reduction of M cation in the
structure from Mn+ ĺ0(n-1)+ (n = 3 or 4) to generate ȕ-O2 desorption site and anion vacancy
generate in the bulk after desorption of lattice oxygen from the surface
1
M n O 2 M n o M ( M1) V0 M ( n 1) O 2
2
(5)
Thereafter, ȕ-oxygen desorption involves the diffusion of oxygen from the bulk through the
desorption site at the surface of the structure:
( n 1)
( n 1)
n 1)
n 1)
n
n
M surface
V0 M surface
M nbulk
O 2 M nbulk

o M surface
O 2 M surface
M (bulk
V0 M (bulk
(6)
The substitution of cobalt by Cu2+ leads to a positive charge deficiency which is compensated
by oxygen vacancies. 7KHĮ-O2 desorption is related to O2 adsorbed on anion vacancies which
FDQ EH GHVRUEHG DW UHODWLYHO\ ORZ WHPSHUDWXUH 7KH HQKDQFHPHQW RI Į-O2 desorption by Cu
substitution implies that the density of oxygen vacancies was increased by increasing the Cu
substitution percentage because copper substitution would yield additional adsorption sites
such as Cu 2 O , Cu 2 O 2 and Cu V0 . Generally, O2-TPD profiles for M-based perovskites
UHYHDO WKDW &X VXEVWLWXWLRQ QRW RQO\ HQKDQFHV Į-O2 desorption due to an increase in surface
oxygen vacancies but it also enhances the mobility of lattice O -2 because of the higher
reducibility of copper. In the case of Cu- and Pd-substituted samples, the desorption of ȕ-O2
can also be realized via the following step:
1
( n 1)
( n 1)
n
n
M surface
O 2 Bsurface

o M surface
V0 Bsurface
O2
2
B= Cu or Pd
(7)
Appendix ± VII
Thermodynamic Analysis of CO oxidation
Thermodynamic analysis of CO oxidation reaction
CO oxidation reaction
CO (g) + ½ O2 (g)
CO2 (g)
(8)
For the heat capacity equation
Cp ¨D¨E7¨F72 ¨G7-2
'a
>¦ n a @
>¦ n a @
'b
>¦ n b @
>¦ n b @
'c
>¦ n c @
>¦ n c @
'd
>¦ n d @
i
i Pr oducts
i i Pr oducts
i i Pr oducts
i
i Pr oducts
i
(9)
i Re ac tan ts
i i Re ac tan ts
i i Re ac tan tss
>¦ n d @
i
i Re ac tan ts
Heat capacity data
c×106
b×103
Component
a
CO(g)
3.376
0.557
O2(g)
3.639
0.506
CO2(g)
5.457
1.045
Source: J. M. Smith, H. C. Van Ness, M. M. Abbott, Introduction
d×10-5
-0.031
-0.227
-1.157
to Chemical Engineering
Thermodynamics, Fifth edition, McGraw Hill International edition, Table C1, pp. 638
Component
'H 0f 298
'G 0f 298
(J/mol)
(J/mol)
CO(g)
-110525
-137169
O2(g)
CO2(g)
-393509
-394359
Source: J. M. Smith, H. C. Van Ness, M. M. Abbott, Introduction to Chemical Engineering
Thermodynamics, Fifth edition, McGraw Hill International edition, Table C4, pp. 640
>¦ n a @
'a
i
>¦ n a @
i Pr oducts
i
i Re ac tan ts
= 5.457 ± [3.376+ (0.5x3.639)]
= 0.2615
Likewise, other constants can be calculated.
>¦ n b @
'b
i i Pr oducts
>¦ n b @
i i Re ac tan ts
= 1.045x10-3 ± [0.557x10-3+(0.5x0.506x10-3)]
= 0.235x10-3
>¦ n c @
'c
i i Pr oducts
>¦ n c @
i i Re ac tan tss
=0
>¦ n d @
'd
i
i Pr oducts
>¦ n d @
i
i Re ac tan ts
= -1.157x10-5 ± [-0.031x10-5+(0.5x(-0.227x0-5))]
= -1.0125x105
>¦ n H @
0
'H 298
i
0
298i Pr oducts
>¦ n H @
0
298i Re ac tan ts
i
= -393509 ± (-110525+0)
= -282984 J/mol
>¦ n G @
0
'G298
i
0
298i Pr oducts
>¦ n G @
i
0
298i Re ac tan ts
= -394359 ± (-137169+0)
= -257190 J/mol
'G 0
RT
0
'G00 'H 00
RT0
'H 00
RT
1 'C p
dT
T T³0 R
'C p0 dT
³ R T
T0
T
W
T
T0
(10)
257190 (282984)
10.41
8.314 u 298
(282984)
8.314 u 573
0
T
0
T
'C p dT
'G00 'H 00 'H 00 1 T 'C p
dT ³
³
RT0
RT
T T0 R
R T
T0
1
T
59.40
ª
'b 2
'c 3
'd § 1 1 ·º
¨ ¸»
T T02 T T03 «'aT T0 2
3
1 ¨© T T0 ¸¹¼»
¬«
ª
§
'd
'a ln W «'bT0 ¨¨ 'cT02 2 2
W T0
©
¬«
º
·
¸¸W 1»W 1
»¼
¹
0
T
1 'C p
dT
T T³0 R
0
1 T 'Cp
dT
³
R
T
T0
1
T
1 ª
0.235 u 103 §
0
1 ·º
1.0125 u 105 § 1
2
2
3
3
«0.2615573 298 ¨
¸»
¨ 573 298 ·¸ §¨ 573 298 ·¸ ©
¹ 3©
¹
573 «
2
1
© 573 298 ¹»¼
¬
0
T
ª
'b 2
'c 3
'd § 1 1 ·º
¨ ¸»
T T02 T T03 «'aT T0 2
3
1 ¨© T T0 ¸¹»¼
«¬
1 'C p
dT
T T³0 R
1
>71.913 28.144 (163.06)]@
573
= -0.10995
'C p0 dT
³ R T
T0
T
W
ª
§
'd
'a ln W «'bT0 ¨¨ 'cT02 2 2
W T0
©
¬«
º
·
¸W 1»W 1
¸
»¼
¹
T
T0
At temperature 300 0C
W
T
T0
573
298
1.92
'C p0 dT
³ R T
T0
T
ª
§
1.0125 u 10 5
0.2615 ln 1.92 «0.235 u 10 3 u 298 ¨¨ 0 u 298 2 1.92 2 298 2
©
¬
= 0.1706+ [0.07003-0.9031](0.92) = -0.5958
0
·¸1.92 1º1.92 1
¸
¹
»
¼
0
T
'C p dT
'G00 'H 00 'H 00 1 T 'C p
³
dT ³
RT0
RT
T T0 R
R T
T0
'G 0
RT
0
'G573
RT
10.41 59.40 (0.10995) (0.5958)] 48.504
0
'G573
RT
48.504
R = 8.314 (m3 KPa) / (kmol K) = 8.314 J/mol K
0
'G573
0
'G573
RT
48.504 u R u T
48.504 u 8.314 u 573
231069.98
ln K
(11)
K
0
'G573
e RT
K
e 48.504
1.16 u 10 21
The value of K is too large indicates that forward reaction is too fast compared to backward
reaction. It also indicates that the CO oxidation reaction is irreversible in nature. The K value
is very large indicating complete conversion. Reaction
CO (g) + ½ O2 (g)
0
CO2 (g) is exothermic ( 'H 298
= -282984 J/mol) and practically
0
0
=-257190 J/mol; 'S 298
=-86.5 J/mol K)
irreversible up to 1227 0C ( 'G298
Appendix ± VIII
Cost Estimation
Fixed cost
Variable
Man power
cost
Energy cost
Total cost
Reactive grinding
method (RG)
Fixed cost
Variable
Man power
cost
Energy cost
Total cost
Co-precipitation
method (COP)
Fixed cost
Variable
Man power
cost
Energy cost
Total cost
Citrate method (CT)
Preparation
Step
Typical
equipment
Typical
equipment
Muffle
furnace
Medium
Calcination
Low
Dissolution
of metal
salt
precursors
Beaker
with stirrer
Preparation
Step
Typical
equipment
Dissolution
of metal
salt
precursors
Beaker
with stirrer
Low
Preparation
Step
Medium
Pump +
beaker with
stirrer
Precipitation
Low
Stirrer
Mixing
Medium (As fabricated in laboratory)
Low
High
Low
Medium
Muffle furnace
Calcination
High energy ball mill i.e. Planetary ball mill
Buchner
funnel
Filtration
Medium
Medium
Medium
Medium
Washing
Drying
Muffle furnace
Calcination/decomposing
Hot air
Oven
Medium
Drying
Hot air
Distilled
Oven
water on
Buchner
Funnel
Medium
Low
Medium
High
Medium
High
Size reduction with chemical reaction
Electric
heating,
thermostatic
bath
Low
Ageing
Medium
Oil bath
Slow solvent evaporation
Small reactor with H2/N2 or with
simulated gas
High
Activation or activity
High
Small reactor with H2/N2 or with
simulated gas
Activation or activity
Small reactor with H2/N2 or with
simulated gas
High
Activation or activity
The preparation and forming of catalysts on a laboratory scale or manufacture on a commercial scale involved many different steps or unit operations. The
cost estimation of LaCoO3 catalysts on a laboratory scale is reported subjectively below for CO oxidation.
Appendix ± IX
Photograph of Experimental Set-up and
Instruments used for Analysis and
Characterization
Experimental set-up for CO oxidation
Bubble soap meter
Gas chromatography (GC 2010 model, Shimadzu)
TG/DTA (SF 752, Metpler Toledo)
;5';¶SHUW MPD system, Philips)
Surface area analyzer (ASAP 2010, Micromeritics)
Scanning electron microscopy (SEM) (LEO 44 I, JEOL)
Scanning electron microscopy (SEM) (1430 VP, Carl Zeiss)
Transmission electron microscopy (TEM) (Tecnai 20, Philips - Holland)
Temperature programmed reduction (H2-TPR) (AutoChem 2920 analyzer,
Micromeritics)
Temperature programmed reduction (H2-TPR) and Temperature programmed
desorption (TPD-O2) (ChemiSorb 2720, Micromeritics)
Temperature programmed Reduction (H2-TPR) and Temperature programmed
desorption (TPD-O2) (Chemisorption analyzer, Micromeritics)
Zetasizer (Nano ZS, Malvern)