CHEG 211 Chemical Engineering Thermodynamics

Homework #4
Due: July 21, 2017

Not only answers but also how to get to the answers should be shown.

Problem 1)

The heat of dissolution of CaCl2 in water = ∆H
 ∆H

CaCl2 + nH2O
CaCl2 (in nH2O)

Ca + Cl2 + nH2O
CaCl2 (in nH2O), ∆H

Ca + Cl2
CaCl2, ∆H

The heat of dissolution of CaCl2 in water

CaCl2 in 10 mol H2O -862.74 kJ + 795.8 kJ = -66.94 kJ

CaCl2 in 15 mol H2O -867.85 kJ + 795.8 kJ = -72.05 kJ
CaCl2 in 20 mol H2O -870.06 kJ + 795.8 kJ = -74.26 kJ
CaCl2 in 25 mol H2O -871.07 kJ+ 795.8 kJ = -75.27 kJ
CaCl2 in 50 mol H2O -872.91 kJ+ 795.8 kJ = -77.11 kJ
CaCl2 in 100 mol H2O -873.82 kJ+ 795.8 kJ = -78.02 kJ
CaCl2 in 300 mol H2O -874.79 kJ + 795.8 kJ = -78.99 kJ
CaCl2 in 500 mol H2O -875.13 kJ+ 795.8 kJ = -79.33 kJ
Problem 2

Basis of calculation: 1 kg of 15 mass % CaCl2 aqueous solution

Molecular weight of CaCl2 = 110.99

Number of moles of CaCl2 in 1 kg of 15 mass % CaCl2 aqueous solution =1 x 0.15 kg x

mol/0.11099 kg = 1.351 mols

Number of moles of H2O in 1 kg of 15 mass % CaCl2 aqueous solution = 1 x 0.85 x

mol/0.018 kg = 47.222 mols

Molar ratio of H2O to CaCl2 in 1 kg of 15 mass % CaCl2 aqueous solution = 47.222/1.351 =

34.95

CaCl2•6H2O + 28.95H2O
CaCl2 (in 34.95 H2O)

n = 34.95-6 =28.95

Ca + Cl2 + 6H2 + 3O2
CaCl2•6H2O ∆H
 -2607.9 kJ/mol (1)

Ca + Cl2
CaCl2 ∆H  795.8 kJ/mol (2)

CaCl2 + 34.95H2O
CaCl2(in 34.95 H2O) ∆H  76.0 kJ/mol (3)

∆H  6x285.83  

6H2 + 3O2
6H2O (4)

CaCl2•6H2O + 28.95 H2O
CaCl2(in 34.95 H2O), ∆H  ∆H
 ∆H  ∆H  ∆H 
2,607.9  795.8  76.0— 1714.38  21.12 kJ/mol

The number of moles of CaCl2•6H2O required to produce 1 kg of 15 mass % CaCl2 aqueous

solution is 1.351 mols.

0 = 21.12   x 1.351mol  3.28 x 1 kg x t  25

 

• ౥

t = 16.3 oC

Problem 3)
CO + 2H2
CH3OH
Thermodynamic data at 298.15 K and 1 bar
∆fH0, kJ/mol S0, J/(mol K)
CO -110.525 197.674
H2 0 130.684
 CH3OH -200.66 239.81

Cp, (molar heat capacity), J/(mol K) = a +bT +cT2 +dT3

a b c d
CO 3.087x10 -1.285x10-2 2.789x10-5 -1.272x10-8
H2 2.714x10 9.274x10-3 -1.381x10-5 7.645x10-9
CH3OH 2.115x10 7.092x10-2 2.587x10-5 -2.852x10-8

∆rG0 (500K) = ∆rH0 (500K) - 500 x ∆rS0 (500K)

∆rH0 (500K) = ∆rH0 (298.15K) +

∆rCp =-Cp,CO -2Cp,H2 + Cp,CH3OH
= (-3.087 - 2x2.714 + 2.115)x10 + (12.85 - 2x9.274 + 70.92)x10-3T + (-2.789 + 2x1.381 +
2.587)x10-5T2 + (12.72 - 2 x7.645 - 2.852)x10-9 T3
= -64 + 6.5222x10-2T +2.56x10-5T2 -5.422x10-9T3

=
= -6898.0581 J/mol
∆rH0 (298.15K) =-(-110.525) -2x0 +(-200.66) = -90.135 kJ/mol
∆rH0 (500K) = -6.898 - 90.135 = -97.033 kJ/mol

∆rS0 (500K) = ∆rS0 (298.15) +

= = -
18.0394 J/(mol K)
∆rS0 (298.15K) = -197.672 - 2x130.684 + 239.81 = -219.23 J/(mol K)
∆rS0 (500K) = -18.0394 - 219.23 = -237.2694 (J/mol K)
∆rG0 (500K) = -97,033 - 500x(-237.2694) = 21,607 J/mol
Equilibrium constant , K =exp(-∆rG0/RT) = exp(-21,601.7/(8.314x500) =0.00554
=
P0 = 1 bar, P = 1 bar

nCO = nCO,0 - ξ = 1-ξ

nH2 = nH2,0 - 2ξ = 1-2ξ
nCH3OH = nCH3OH,0 + ξ =ξ
nT = 2-2ξ = 2(1-ξ)
yCO =nCO/nT = (1-ξ)/2(1-ξ) = 1/2
yH2 = nH2/nT = (1-2ξ)/2(1-ξ)
yCH3OH =nCH3OH/nT = ξ/2(1-ξ)

By solving the 2nd order equation for ξ,

ξ = 0.00138 or 0.99862
nH2 = 1-2ξ 0.
ξ 0.5
ξ = 0.00138 mols
nT = 2(1-0.00138) = 1.99724 mols
nCO = 1-0.00138 = 0.99862 mols
nCH3OH = 0.00138 mols
yCO = 0.5
yH2 =0.499
yCH3OH =0.00069

Problem 4)
 ∆ G   ∆ G  1x 1,128,790  1x604 , 030  1 x 394,359
J
 130,401
mol
∆ బ
,

K e 
 ౨ 
 e.
  .
  1.423 x 10

Problem 5)

∆H T  ∆H 298.15 K   # υ C,

dT
.


∆H 298.15 K  1x1,206,920  1x635,090  1 x393,509

J
 178,321
mol

# υ C,

dT
J ∆B  1 1
.


 8.314
'∆AT  298.15  T  298.15   ∆D +  ,-
mol K 2 T 298.15
∆A  1x12.572  1x6.104  1x5.457  1.011
∆B  '1x2.637  1x0.443  1x1.045-x10  1.149x10
∆D  ''1x3.12  1x1.047  1x1.157-x10  0.916x10

∆S T  ∆S 298.15 K   # υ C,

/T dT
.


∆H 298.15 K  ∆ G 298.15 K 178,321  130,401

∆S 298.15 K  
T 298.15
J
 160.724
mol • K

 # υ C,

/T dT
J T
.


 8.314 '∆Axln  ∆B1T  298.15 2

mol K 298.15
1 1
 ∆D/2x +   ,-
T 298.15

∆G T  ∆H T  T x ∆S T

lnK  ∆G T/RT

Following the above procedure, calculate lnK with varying T up to 2000 K using MatLAB.

Temperature
T, K 1/T, K-1 lnK
x 103
298.15 3.354 -52.607
400 2.500 -34.311
500 2.000 -23.643
600 1.667 -26.571
700 1.429 -11.554
 800 1.250 -7.8029
900 1.111 -4.9410
1000 1.000 -2.6601
1100 0.909 -0.8121
1200 0.833 0.7113
1300 0.769 1.9854
1400 0.714 3.6064
1500 0.667 3.9866
1600 0.625 4.7826
1700 0.588 5.4746
1800 0.556 6.0810
1900 0.526 6.6130
2000 0.500 7.0843

Problem 6)

a ! a !మ p !మ
K   p !మ
a !య P
T = 1500 + 273.15 = 1773.15 K
lnK = 5.4746 at 1700 K
K = 238.8
lnK = 6.081 at 1800 K
K = 437.5

Because the operating p !మ , which must be no higher than the system pressure, is below the
equilibrium p !మ , the reaction continues to move in the forward direction to increase the
pressure, according to Le Chatelier’s principle, until CaCO3 is completely decomposed into
CaO and CO2.

Problem 7)

n మ "ర  n మ "ర ,  1ε
 1ε  2  ε
 ε

n"మ  n"మ ,  1/2ε
 3ε  5  0.5ε
 3ε
n మ "ర !  n మ "ర !,  ε
 ε

n !మ  n !మ ,  2ε  1  2ε
n"మ !  n"మ !,  2ε  2ε
ε
 0.3, ε  0.5
n మ "ర  2  0.3  0.5  1.2 mol
n"మ  5  0.5x0.3  3x0.5  3.35 mol
n మ "ర !  0.3 mol
n !మ  1  2x0.5  2 mol
n"మ !  2x0.5  1 mol

n  n మ "ర  n"మ  n మ "ర !  n !మ  n"మ !  1.2  3.35  0.3  2  1  7.85 mol

1.2
y మ "ర   0.153
7.85
3.35
y "మ   0.427
7.85
0.3
y మ "ర !   0.038
7.85
2
y !మ   0.255
7.85
1
y "మ !   0.127
7.85

Problem 8)
౯ి ౌ ౯ీ ౌ

K
 
ౌబ ౌబ #ి #ీ
౯ ఽ ౌ౯ ా ౌ
#ఽ #ా
ౌబ ౌబ
y$ P 
  y$
K  P 
y% P y P y% y
P P
n%  n%,  1ε
 1ε  2  ε
 ε
n&  n&,  1ε
 1  ε

n  n ,  ε
 ε  ε
 ε
n'  n',  ε
 ε

n$  n$,  2ε  2ε
n  2  ε
 ε   1  ε
  ε
 ε   ε
 2ε  3
y%  2  ε
 ε /3
y&  1  ε
/3
y  ε
 ε /3
y'  ε
/3
y$  2ε /3

K1 = 2.667, K2 = 3.2

y y' ε
 ε /3xε
/3 ε
 ε ε

2.667   
y% y& 2  ε
 ε /3x1  ε
/3 2  ε
 ε 1  ε

y$
2ε /3 
4ε
3.2   
y% y 2  ε
 ε /3xε
 ε /3 2  ε
 ε ε
 ε 

By solving the two equations simultaneously,

Calculated values of NLE variables

Variable Value f(x) Initial Guess
1 e1 0.8341628 5.456E-10 0.5
2 e2 0.4598197 3.291E-11 0.1

Nonlinear equations
1 f(e2) = -3.2 + 4*e2^2/((2-e1-e2)*(e1-e2)) = 0
2 f(e1) = -2.667+(e1-e2)*e1/((2-e1-e2)*(1-e1)) = 0

ε
 0.834
ε  0.460

2  0.834  0.460
y%   0.235
3
1  0.834
y&   0.055
3
0.834  0.460
y   0.125
3
0.834
y'   0.278
3
2x0.460
y$   0.307
3

Problem 9)

∆G for H2 (at 1 atm) + O2 (at 0.21 atm)
H2O ( at 1atm) is composed of two steps.
(1) ∆G
for conversion of O2 (at 0.21 atm) to O2 (at 1 atm)
(2) ∆G  228,572 J/mol
∆G
 ∆H
 T∆S

H,

(
T, P  H,
T, p 
∆H
 0
C R
dS  dT  dP
T P
p
∆S  S,
T, p   S,
T, P  Rln
P
 R

∆S
 #  dP  Rln0.21
P
J J
.

∆G
 ∆H
 T∆S
 0  298.15x8.314 ln0.21  3868.6

mol K mol of O

J J
∆G  ∆G
 ∆G  3868.6  228,572
mol of O mol of extent of reaction

J 0.5 mol of O
 3868.6
mol of O mol of extent of recation
J J
 228,572  226,638
mol of extent of reaction mol

∆G  226,638  2x96,485.3 E
E  1.174 V
∆H  241,818 J/mol
Q  ∆H  W  241,818  226,638  15,180


(lost to surroundings)

Problem 10)

y)! P
γ")!య x")!య   
K P
y)!మ P 
  γ"మ !x"మ ! 
P
∆ G  3x 51,310  1x237,129  2 x 111,250  1 x 86550

J
 52,751
mol
,*

K  e.
.
  1.7x10


Basis of calculation: 1 kg of 50 wt% of HNO3

Number of moles of water = 500/18 = 27.78 mol
Number of moles of HNO3 = 500/63=7.937 mol
7.937
x")!య   0.222
7.937  27.78
x"మ !  1  0.222  0.778
ε: extent of reaction
n, : number of moles of feed to the reactor
n)!మ  0.25n,  3ε
n)!  0.1n,  ε
n!మ  0.3n,
n+  0.35n,

n"మ !  27.78  n"మ !,  ε

n")!య  7.937  0  2ε
7.937
ε  3.968 mol
2
Total number of moles of species in the gas phase at equilibrium: nT

n  n)!మ  n)!  n!మ  n+  (0.25n,  3ε  C0.1n,  εD  0.3n,  0.35n, 

n,  2ε
y)!మ  0.25n,  3ε/n,  2ε
y)!  0.1n,  ε/n,  2ε
y!మ  0.3n, /n,  2ε
y+  0.35n, /n,  2ε

y)! P
γ")!య x")!య  
  0.5785x0.222 0.1n,  ε/n,  2ε
K P   1.7x10

y)!మ P 
   γ"మ !x"మ !  '0.25n,  3ε/n,  2ε- 0.027x0.778

P
ε  3.968 mol

Solve for NT,0. K value is too high to be solved with Polymath. For such a high K value, the
reaction is nearly irreversible and a complete conversion of NO2 could be assumed.
n)!మ  0.25n,  3ε  0
0.25n,  3x3.968  0
n,  47.616 mol

y)!మ  0
0.1n,  ε
y)!   0.22
n,  2ε
y!మ  0.3n, /n,  2ε  0.36
y+  0.35n, /n,  2ε  0.42