Heat Capacites

Cp=A+bT+cT2+dT3

[Yaws, C.L., Chemical Properties Handbook: Physical, Thermodynamic, Environmental,

Transport, Safety, and Health Related Properties for Organic and Inorganic Chemicals,
McGraw-Hill, 1995.]

Component a (J/mol.K) b (J/mol.K) c (J/mol.K) d (J/mol.K)

C 8 H 10 0.182 5.1344x10-1 -2.02x10-4 -2.1615x10-8

(o-xylene)
C 8 H 4 O3 40.083 3.6084x10-2 9.5956x10-4 -1.234x10-6
(phthalic anhydride)
O 2(oxygene) 29.526 -8.8999x10-3 3.8083x10-5 3.2629x10-8

C 4 H 2 O3 -72.015 1.0423 -1.8716x10-3 1.6527x10-6

(maleic anhydride)
H 2 O(water) 33.933 -8.4186x10-3 2.9906x10-5 -1.7825x10-8

C O2 27.437 4.2315x10-2 -1.955x10-5 3.9968x10-9

(carbon dioxide)
N 2(nitrogene) 29.342 -3.5395x10-3 1.0076x10-5 -4.3116x10-9

∆ CpC 8 H 10 =¿0.182 + 5.1344x10-1T - 2.02x10-4T2 - 2.1615x10-8T3

∆ CpC 8 H 4 O3 = 40.083+ 3.6084x10-2T +9.5956x10-4T2 – 1.234x10-6T3

∆ CpO = 29.526 – 8.89994x10-3T + 3.8083x10-5T2 + 3.2629x10-8T3

2

∆ CpC 8 H 2O 3 =¿ -72.015 + 1.0423T – 1.8716x10-3T2 + 1.6527x10-6T3

∆ Cp H O = 33.933 – 8.4186x10-3T + 2.9906 x10-5T2 – 1.7825x10-8T3

2

∆ CpCO = 27.437 + 4.2315x10-2T – 1.955x10-5T2 + 3.9968x10-9T3

2

∆ Cp N = 29.342 – 3.5395x10-3T + 1.0076x10-5T2 – 4.3116x10-9T3

2

 C8H10 + 3O2 → C8H2O3 + 3H2O (Main Reaction)

∆ Cp ( molK
joule
)=∆ a+∆ bT + ∆ c T + ∆ d T 2 3

∆ Cp=∆ Cp products −∆ Cpreactants

∆ Cp ¿(∆ CpC H 8 4
O3 +3 x ∆ CpH O )−¿ +3 x ∆ CpO ¿
2 2

∆ a=∆ a products −∆ areactants

∆ a=( 40.083+3 x ( 33.933 ) )−¿ 53.122

∆ b=∆ b products −∆ b reactants

∆ b=( 3.6084 x 10 + 3 x (−8.4186 x 10 ) ) −¿

−2 −3

∆ b=−0.4759 12

∆ c=∆ c products −∆ c reactants

∆ c=¿ ( 9.5956 x 10−4 +3 x ( 2.9906 x 10−5 ) ) −¿

∆ c=¿ 1.13702x10-3

∆ d=∆ d products −∆ d reactants

∆ d=¿ (−1.234 x 10−6+ 3 x (−1.7825 x 10−8 ) ) −¿

∆ d=¿-1.3637x10-6

∆ Cp=(53.122)+(−0.475912)T + ( 1.13702 x 10−3 ) T 2 +(−1.3637 x 10−6)T 3 was found.

 C8H10 + 7.5O2 → C4H2O3 + 4H2O + 4CO2 (Side Reaction)

∆ Cp ( molK
joule
)=∆ a+∆ bT + ∆ c T + ∆ d T 2 3

∆ Cp=∆ Cp products −∆ Cpreactants

∆ Cp ¿(∆ CpC H 8 2
O3 +7.5 x ∆ CpH O )−¿ + 4 x ∆ CpH O +4 x ∆ CpO ¿
2 2 2
∆ a=∆ a products −∆ areactants

∆ a=¿ -48.162

∆ b=∆ b products −∆ b reactants

∆ b=( 1.0423+4 x (−8.4186 x 10 ) + 4 x ( 4.2315 x 10 ) )−¿

−3 −2

∆ b=0.731

∆ c=∆ c products −∆ c reactants

∆ c=¿ (−1.8716 x 10−3 + 4 x ( 2.9906 x 10−5 ) + 4 x ( −1.955 x 10−5 ) ) −¿

∆ c=¿ -2.116x10-3

∆ d=∆ d products −∆ d reactants

∆ d=¿ ( 1.6527 x 10−6 + 4 x ( 2.9906 x 10−5 ) + 4 x ( 3.9968 x 10−9 ) )−¿

∆ d=¿ 1.43 x10-6

∆ Cp=(−48.162)+(0.731)T + (−2.116 x 10−3 ) T 2+(1.43 x 10−6)T 3 was found.

Enthalpy and Gibbs Energy of Formation

Yaws, C.L., Chemical Properties Handbook: Physical, Thermodynamic, Environmental,

Transport, Safety, and Health Related Properties for Organic and Inorganic Chemicals,
McGraw-Hill, 1995.

o o
Component ∆ H f ,298 (kJ /mol) ∆ G f ,298 (kJ /mol)
C 8 H 10 ( o−xylene ) 19.0 kJ/mol 122.09 kJ/mol
C 8 H 4 O3 ( pt h alic an h ydride) -393.14 kJ/mol -329.00 kJ/mol
O2 (oxygene) 0 0
C 4 H 2 O3 (maleic an h ydride) -398.30 kJ/mol -355.00 kJ/mol
H 2 O(water ) -241.8 kJ/mol -228.60 kJ/mol
C O2 (carbon dioxide) -393.5 kJ/mol -394.4 kJ/mol
  C8H10 + 3O2 → C8H2O3 + 3H2O (Main Reaction)

o o o
∆ H r ,298 =∆ H f , products −∆ H f , reactants
o o o o o
∆ H r ,298 =( ∆ H f ,C H 8 4
O3 + 3∗∆ H f , H O )−(∆ H f ,C H +3∗∆ H f ,O )
2 8 10 2

o
((
∆ H r ,298 = −393.14
kJ
mol ) (
+ 3∗ −241.8
kJ
mol
− 19.0
kJ
mol
+3∗0 ¿−1137.54 )) ((
kJ
mol ) )

o o o
∆ Gr ,298 =∆ G f , products −∆G f , reactants

∆ Gro,298 =( ∆ Gof ,C H 8 4 O3 +3∗∆G of , H 2 O )−( ∆ Gof , C H8 10

+3∗∆ Gof ,O )2

o
((
∆ Gr ,298 = −329.0
kJ
mol ) (
+ 3∗ −228.60
kJ
mol
− 122.09
kJ
mol )) ((
+3∗0 = -1136.89
kJ
mol ) )
Equilibrium Constant

Tref is 25°C = 298K

T
+ ∫ ∆ CpdT
o o
∆H r ,T =∆ H r ,298
298

∆ Cp=(53.122)+(−0.475912)T + ( 1.13702 x 10−3 ) T 2 +(−1.3637 x 10−6)T 3

(∫ ( )
T
J
53.122−0.475912 .T +1.13702 x 1 0 T −1.3637 x 10 . T ) dT J /mol . K
o −3 2 −6 3
∆ H r ,T =−1137540 +
mol 298

o 2 −4 3 −7 4 J
∆ H r ,T =−1137540+ 53.122T −0.237956 T +3.79 x 10 T −3.4 x 10 T
mol

o
−∆ Gr ,298
ln K 298 =
RT
 J
−(−1136890 )
mol
ln K 298 = =458.87
( 8.314
J
mol . K
(298 K ) )
°
dlnK ∆ H r
= 2
Van’t Hoof Equation
dT RT
T o
1 ∆ H r ,T
ln K T =ln K 298 + ∫
R 298 T 2
dT

1
lnKT = lnK298 + 8.314 J x
mol . K
T

[ ∫ ¿ ¿ ¿]
298

ln K T =458.87 +53.122 ( ln |T|)−1.133 x 10 T +1.695 x 10 T −0.237956 T +1137540T

−7 3 −4 2 −1

 C8H10 + 7.5O2 → C4H2O3 + 4H2O + 4CO2 (Side Reaction)

o o o
∆ H r ,298 =∆ H f , products −∆ H f , reactants
o o o o o o
∆ H r ,298 =( ∆ H f ,C H 8 4
O3 + 4∗∆ H f , H O +4∗∆ H f ,co )−(∆ H f ,C
2 2 8
H10 +7.5∗∆ H f ,O ) 2

o
((
∆ H r ,298 = −398.30
kJ
mol ) (
+ 4∗ −241.8
kJ
mol
+4∗ −393.5
kJ
mol
− −19.0
kJ
) (
mol
+7.5∗0 )) ( ( ) )
kJ
¿
mol

o
∆ H r ,298 = -2958.5kJ/mol = -2546360 J/mol

o o o
∆ Gr ,298 =∆ G f , products −∆G f , reactants

∆ Gro,298 =( ∆ Gof ,C H 8 4 O3 + 4∗∆ G of , H O +4∗∆ Gof , CO )−( ∆ Gof ,C H +7.5∗∆ Gof ,O )

2 2 8 10 2
 o
((
∆ Gr ,298 = −355.0
kJ
mol ) (
+ 4∗ −228.60
kJ
mol ) (
+ 4∗ −394.4
kJ
mol
− 122.09
kJ
mol )) ((
+7.5∗0 = - ) )
2569.09 kJ/mol = -2569090 J/mol
Equilibrium Constant

Tref is 25°C = 298K

T
∆ H r ,T =∆ H r ,298 + ∫ ∆ CpdT
o o

298

∆ Cp=(−48.162)+(0.731)T + (−2.116 x 10−3 ) T 2+(1.43 x 10−6)T 3

(∫ ( )
T
−48.162+0.731 . T −2.116 x 10 .T +1.43 x 10 . T ) dT J /mol . K
o −3 2 −6 3
∆H r ,T =−2546360+
298

o 2 −4 3 −7 4 J
∆ H r ,T =−2546360−48.162 T +0.3655 T −7.053 x 10 T +3.575 x 10 T
mol

o
−∆ Gr ,298
ln K 298 =
RT
J
−(−2569090 )
mol
ln K 298 = =¿ 1036.94
( 8.314
J
mol . K
(298 K ) )
°
dlnK ∆ H r
= 2
Van’t Hoof Equation
dT RT
T o
1 ∆ H r ,T
ln K T =ln K 298 + ∫ dT
R 298 T 2

1
lnKT = lnK298 + J x
8.314
mol . K
T 2 −4 3 −7 4
∫ ( −2546360−48.162 T +0.3655 TT−7.053
2
x 10 T +3.575 x 10 T
¿ ) dT ¿
298

lnKT = 1036.94 + 1/8.314 (2546360/T – 48.162ln(T) + 1.19167x10-7T3 -3.5265x10-4 + 0.365)