Svnas 8e Ism Chapter 04

SVNAS 8th Edition Annotated Solutions Chapter 4
4.1.(7th edition prob. 4.1)

If we have set up a spreadsheet to evaluate the heat capacity integral like the example spreadsheet from the
lecture notes, we can use it to evaluate the heat capacity integral in each case, and simply enter the heat
capacity parameters and read out the value of the integral:
T
 T  T0 

CP B

dT = A T  T0  + T 2  T02 +
C 3
 
T  T03 + D   
T0
R 2 3  TT0 
T
CP
 dT  ICPH T0 , T , A, B, C , D 
T0
R
Q = H = n × R × ICPH
(a) If 10 mol of SO2 is heated from 200 to 1100C, the heat requirement will be 10*R*ICPH, where ICPH
is the heat capacity integral. Using our spreadsheet to evaluate ICPH, we get
T1 (K) T2 (K) A B (1/K) C (1/K ) D (K ) ICPH (K)
2 2
473.15 1373.15 5.699 8.01E-04 0 -1.02E+05 5.65E+03

So, the heat requirement is 10 mol*8.314 J mol K *5650 K = 469700 J = 470 kJ
-1 -1
(b) Similarly, if we heat 12 moles of propane from 250 to 1200 C, the heat requirement is 12*R*ICPH.
Putting the heat capacity parameters for propane and these temperatures into the ICPH spreadsheet
gives
T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPH (K)
523.15 1473.15 1.213 2.88E-02 -8.82E-06 0.00E+00 1.95E+04
So, the total heat requirement is 12 mol*8.314 J mol-1 K-1*19500 K = 1.95106 J = 1950 kJ
4.2 (7th edition Prob. 4.2)

lecture notes, we can use it to evaluate the heat capacity integral in each case, and simply vary the final
temperature until we get the desired Q.
(a) If 800 kJ is added to 10 mol of ethylene, then Q = H = 800000 J/10 mol = 80000 J mol . So, H/R =
-1
80000 J mol-1 /8.314 J mol-1 K-1 = 9622 K, so the integral of Cp/R from 200C (473 K) to the final
temperature should be 9622 K. Using our spreadsheet to evaluate this, we get
Updated 18/01/2017 1
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473 1374.4 1.424 1.44E-02 -4.39E-06 0.00E+00 9.622E+03
So, the final temperature is 1374 K.
(b) Similarly, if we add 2500 kJ to 15 mol of 1-butene, we have H/R = 2500000 J / (15 mol *8.314 J mol-
1
K-1 )= 20045 K. Putting the heat capacity coefficients for 1-butene into the spreadsheet and trying
final temperatures until we get this value, we get
533 1414 1.967 3.16E-02 -9.87E-06 0.00E+00 2.005E+04
So, the final temperature is 1414 K.
(c) This is the same, but in English units, in which we can use R = 1.986 Btu lbmol-1 R-1, so H/R = 106
Btu / (40 lbmol *1.986 Btu lbmol-1 R-1) = 12588 R = 6993 K. The initial temperature of 500 F is 533
K. So, we get
533 1202.7 1.424 1.44E-02 -4.39E-06 0.00E+00 6.994E+03
And the final temperature is 1203 K = 1705 F.
4.3 (New)
To compute the outlet temperature, use
But first the heat capacity at 373.15 K must be determine for each compound using the Table C.1 and Eqn
4.5.
This can easily be done in a spreadsheet.

T out
species A 103 B 106 C 10−5 D Cp *R (K)
a Methane 1.702 9.081 -2.164 0 4.79 39.82 674.52
b Ethane 1.131 19.225 -5.561 0 7.53 62.61 564.82
c Propane 1.213 28.785 -8.824 0 10.73 89.17 507.72
-
d n-Butane 1.935 36.915 11.402 0 14.12 117.41 475.35
-
e n-Hexane 3.025 53.722 16.791 0 20.73 172.38 442.76
-
f n-Octane 4.108 70.567 22.208 0 27.35 227.37 425.93
Updated 18/01/2017 2
g Propylene 1.637 22.706 -6.915 0 9.15 76.05 530.95

-
h 1-Pentene 2.691 39.753 12.447 0 15.79 131.29 464.55
-
i 1-Heptene 3.768 56.588 17.847 0 22.40 186.22 437.59
-
j 1-Octene 4.324 64.96 20.521 0 25.71 213.72 429.30
k Acetylene 6.132 1.952 0 -1.299 6.86 57.04 583.54
- -
l Benzene 0.206 39.064 13.301 0 12.52 104.08 488.45
m Ethanol 3.518 20.001 -6.002 0 10.15 84.35 515.41
-
n Styrene 2.05 50.192 16.662 0 18.46 153.47 451.34
o Formaldehyde 2.264 7.022 -1.877 0 4.62 38.43 685.37
p Ammonia 3.578 3.02 0 -0.186 4.70 39.12 679.92
Carbon
q monoxide 3.376 0.557 0 -0.031 3.58 29.80 775.89
r Carbon dioxide 5.457 1.045 0 -1.157 5.85 48.61 620.01
s Sulfur dioxide 5.699 0.801 0 -1.015 6.00 49.87 613.79
t Water 3.47 1.45 0 0.121 4.01 33.35 732.99
u Nitrogen 3.28 0.593 0 0.04 3.50 29.11 785.38
Hydrogen
v cyanide 4.736 1.359 0 -0.725 5.24 43.59 648.43

Looking in table A.2, we are reminded that the gas constant is R = 0.7302 ft3 atm (lb mol)-1 R-1 in the sort
of units used in this problem, so we can convert the volumetric flow rate to a molar flow rate using the ideal
gas law (air at atmospheric conditions is very nearly an ideal gas).
n = PV/RT = 1 atm * 250 ft s / (10.7302 ft atm lbmol R * (122R + 459.7R ) =
3 -1 3 -1 -1
n = 0.59 lbmol s-1

To find the heat needed to heat the air at constant pressure from 122F to 932 F, we need to integrate the
heat capacity over that temperature range
932 F
Q

122 F
nC p dT
The ideal gas heat capacity for air is given in table C.1 as

C p  R A  BT  DT 2 
Updated 18/01/2017 3
T must be in Kelvins for use in this expression, so we convert 122F to 323.15 K and 932 F to 773.15 K.
We then have
773 K
Q  nR

323 K
A  BT  DT 2 dT
773 K
 B D
Q  nR  AT  T 2  
 2 T  323 K
Putting in n = 0.59 lbmol s , R = 1.986 Btu lbmol-1 R-1, A = 3.355, B = 0.57510-3 K-1, D = -1600 K2 gives
-1


 

 1
Q  0.59 lbmol s-1 *1.986 Btu lbmol-1 R -1 3.355  773  323  2.88  104 7732  3232  1600 
773

1 
323   K  1.8 R/K

Q  3478 Btu s-1
Note that because the heat capacity integral comes out with units of K, while we are using R with units of
R, we have to multiply by 1.8 R/K.
4.5 (7th edition Prob. 4.4) How much heat is required when 10,000 kg of CaCO3 is heated at atmospheric
pressure from 50°C to 880°C?
The number of moles of CaCO3 is 10 g/ 100.09 g mol = 99910.08 mol CaCO3. Evaluating the heat
7 -1
capacity integral from 323 to 1153 K, we get H/R = 11350 K

323 1153 12.572 2.64E-03 0.00E+00 -3.12E+05 1.182E+04
So, 99910.08 mol * 8.314 J mol K * 11350 K = 9.43109 J = 9.43106 kJ.
-1 -1
4.6. (7 edition prob. 4.5)

th
For consistency with the problem statement, we rewrite Eq. (4.8) as:
C   A  B2 T   1  C3 T 
p 1 1
2 2
 1
where T2/T1. DefineCPam as the value of CP evaluated at the arithmetic mean temperature Tam.
Then:
Where
Whence,
Updated 18/01/2017 4
Define δ as the difference between the two heat capacities:
This readily reduces to:

Making the substitution τ = T2/T1 yields the required answer.
𝑇2/𝑇1 = 𝑇2 𝑇1
4.7. (7th edition prob. 4.6)
For consistency with the problem statement, we rewrite Eq. (4.8) as
C   A  B2 T   1   DT
p 1 2
1
where τ ≡ T2/ T1. Deﬁne CPam as the value of CP evaluated at the arithmetic mean
temperature Tam.
As in the preceding problem,
Whence,
Define δ as the difference between the two heat capacities:
This readily reduces to:
Updated 18/01/2017 5
Making the substitution τ = T2/ T1 yields the required answer.
𝑇1
𝑇1
4.8. (7th edition prob. 4.7)

Let step 12 represent the initial reversible adiabatic expansion, and step 23
the final constant-volume heating.
Given
R /Cp
P 
T2  T3  2 
 P3 
Solve for Cp
4.9 (7th edition prob. 4.8)

Except for the noble gases [Fig. (4.1)], CP increases with increasing T . Therefore, the estimate is
likely to be low.

(a) In this part, we use equation 4.14
reduced temperature at another reduced temperature. The critical temperature for n-pentane (from appendix
B) is 469.7 K. So, 25C corresponds to a reduced temperature of Tr1 = 298.15/469.7 = 0.6348. The normal
boiling point for n-pentane (also from appendix B) is 309.2 K, which corresponds to a reduced temperature
Tr2 = 309.2/469.7 = 0.6583. So, using equation 4.14, we have
Updated 18/01/2017 6
0.38
 1  Tr 2   1  0.6583 
0.38
H 2  H1    366.3    357.1 J g -1

 1  Tr1   1  0.6348 
This is essentially exact agreement with the handbook value (it differs by 0.03%).
(b) In this part, we estimate the heat of vaporization at the normal boiling point without using the
information on the heat of vaporization at 25C, using equation 4.13
also use the critical pressure, Pc = 33.70 bar for n-pentane. Then, using equation 4.13:
 1.092  ln Pc  1.013   1.092  ln 33.7  1.013 
H n  RTn    8.314*309.2    25876 J mol
-1
 0.930  Trn   0.930  0.6583 

Dividing by the molecular weight of n-pentane (72.15 g/mol) gives Hn = 358.6 J g . This is just 0.4%
-1
higher than the handbook value, and it only required knowledge of the critical properties and the normal
boiling point temperature.
4.11. (Like 7th edition 4.10, but in different units, solutions below are for 7th edition version and
We want to evaluate the latent heat of vaporization using the Clapeyron equation:
dP sat
H  T V
dT
(a) At -16C, we see that the vapor volume is 0.12551 m3kg-1 and the liquid volume is 0.000743 m3kg-
1
, so V = 0.124767 m3kg-1. Now, we can estimate the slope of the vapor pressure curve from the
values at -18, -16, and -14 C, which are 1.446,1.573, and 1.708 bar, respectively. So, we could
estimate the slope as
dP sat P 1.708bar  1.446bar
   00.0655bar.K -1  0.0655*102 kPa.K 1
dT T (273.15  (14)) K  (273.15  (18)) K
So, we have
H  (273.15  (16))K *0.124767m3.kg 1 *0.0655*102 kPa.K1  210.4kPa.m3 .kg1  210.4kJ.kg1
(b) At 0C, we see that the vapor volume is 0.069309 m3kg-1 and the liquid volume is 0.000722 m3kg-
1
values at -2, 0, and 2 C, which are 2.722,2.928, and 3.146 bar, respectively. So, we could estimate
the slope as
   0.106bar.K -1  0.106*102 kPa.K 1
dT T (273.15  (2)) K  (273.15  (2)) K
So, we have
Updated 18/01/2017 7
H  (273.15  (0))K *0.068587m3.kg 1 *0.106*102 kPa.K 1  198.59kPa.m3 .kg1  198.59kJ.kg1
(c) At 12C, we see that the vapor volume is 0.046332 m3kg-1 and the liquid volume is 0.000797 m3kg-
1
values at 10, 12, and 14 C, which are 4.146,4.43, and 4.732 bar, respectively. So, we could
   0.1465bar.K -1  0.1465*102 kPa.K 1
dT T (273.15  (14)) K  (273.15  (10)) K
So, we have
H  (273.15  (12))K *0.045535m3.kg 1 *0.1465*102 kPa.K 1  190.22kPa.m3 .kg1  190.22kJ.kg1
(d) At 26C, we see that the vapor volume is 0.029998 m3kg-1 and the liquid volume is 0.000831 m3kg-
, so V = 0.029167 m kg . Now, we can estimate the slope of the vapor pressure curve from the
1 3 -1
values at 24, 26, and 28 C, which are 6.458,6.854, and 7.269 bar, respectively. So, we could
   0.20275bar.K -1  0.20275*102 kPa.K 1
dT T (273.15  (28)) K  (273.15  (24)) K
So, we have
H  (273.15  (26)K *0.029167m3.kg 1 *0.20275*102 kPa.K 1  176.91kPa.m3 .kg1  176.91kJ.kg1
(e) At 40C, we see that the vapor volume is 0.019966 m3kg-1 and the liquid volume is 0.000872 m3kg-
1
values at 35, 40, and 45 C, which are 8.87, 10.166 and 11.599 bar, respectively. So, we could
   0.2729bar.K -1  0.2729*102 kPa.K 1
dT T (273.15  (45)) K  (273.15  (35)) K
So, we have
H  (273.15  (40)K *0.019094m3.kg 1 *0.2729*102 kPa.K 1  163.17kPa.m3 .kg1  163.17kJ.kg1
Updated 18/01/2017 8
(a) Equation 4.14 is used to estimate the latent heat at a temperature of interest from the (known) latent
heat at some other temperature, and may be written as:
0.38
 1  Tr 2 
H 2  H1  
 1  Tr1 
For chloroform, the critical temperature is 536.4 K and the normal boiling point is 334.3 K. At 273 K, Tr1
= 0.5089 and at 334.3 K, Tr2 = 0.6232. So,
0.38
 1  0.6232 
H 2  270.9 J g-1    245.0 J g -1
 1  0.5089 
This is 0.8% lower than the handbook value.
Similarly for methanol, Tr1 = 0.5326 and Tr2 = 0.6592, so
0.38
 1  0.6592 
H 2  1189.5 J g-1    1055.0 J g-1
 1  0.5326 
This is 4.1% below the handbook value.
Similarly for tetrachloromethane (also known as carbon tetrachloride!), Tr1 = 0.4909 and Tr2 = 0.6287, so
0.38
-1  1  0.6287 
H 2  217.8 J g    193.2 J g-1
 1  0.4909 
This is 0.5% below the handbook value.
(b) Equation 4.13 is used to estimate the heat of vaporization at the normal boiling point without knowing
the heat of vaporization at any temperature. It can be written as
 1.092  ln Pc  1.013 
H n  RTn  
 0.930  Trn 
 
where Pc, the critical pressure, must be given in bar. For chloroform, we get
 1.092  ln  54.72   1.013 
H n  8.314 J mol-1 K -1 334.3 K    29570 J mol-1
 0.930  0.6232 
 
dividing by the molecular weight of 119.4 g mol-1 gives 247.7 J g-1. This is just 0.3% above the handbook
value.
Likewise, for methanol:

 1.092  ln 80.97   1.013 
H n  8.314 J mol-1 K -1* 337.9 K    38302 J mol-1
 0.930  0.6592 
 
and dividing by the molecular weight of 32.042 g mol gives 1194.2 J g-1. This is 8.6% above the handbook
-1
value.
Updated 18/01/2017 9
Finally, for carbon tetrachloride,

 1.092  ln  45.6   1.013 
H n  8.314 J mol-1 K -1 349.8 K    29587 J mol-1
 0.930  0.6287 
 
and dividing by the molecular weight of 153.822 g mol gives 192.3 J g-1. This is 1% below the handbook
-1
value.

Again, we want to use the Clapeyron equation to find the latent heat of vaporization from the vapor pressure
curve and molar volumes.
First, we should find the normal boiling point by setting Psat = 101.3 kPa.
Taking the derivative of the Antoine equation for the vapor pressure gives
dP sat d   B  B  B  BP sat
  exp  A    exp  A   
dT dT   T  C   T  C 2  T  C  T  C 2
or, using the numbers for benzene
dP sat 2772.78P sat

dT T  53.00 2
For T = 353.2 K and P = 101.325 kPa this gives
sat
dP sat 2772.78  101.325

  3.118 kPa K -1
dT  353.2  53.00  2
Now, we can use generalized correlations to find the liquid and vapor volumes. The critical properties of
benzene are Tc = 562.2 K, Pc = 48.98 bar,  = 0.210, Zc = 0.271, and Vc = 259 cm mol .
3 -1
For the volume of the saturated liquid, we can use the Rackett equation, which gives
0.2857
 353.2 
1 
V sat  Vc Zc r 
0.2857
1T
 259  0.271 562.2 
 96.8 cm3 mol-1
Since the reduced pressure is only 1.013/48.98 = 0.0207, we expect that the vapor will not be far from
ideal, even though the reduced temperature is only 353.2/562.2 = 0.6282. We can get the compressibility
from the Pitzer correlation as in the previous homework:
0.422
B 0  0.083   0.8049
0.62821.6
0.172
B1  0.139   1.0730
0.62824.2
and
Updated 18/01/2017 10
0.02068
Z  1   0.8049  0.210  1.0730  0.9661
0.6282
So, V = ZRT/P = 0.9661*83.145*353.2/1 = 28370 cm mol .
3 -1
So, V = 28370 --- 82.6 = 28288 cm3 mol-1. Finally, putting this all together, we have
H  353.2 K  28288cm3 mol-1  3.118 kPa K-1  3.115  107 kPa cm3 mol-1  3.115  104 J/mol
So, our final answer is H = 31.15 kJ/mol.
7th edition Prob. 4.12, choose ethylbenzene

We want to use the Clapeyron equation to find the latent heat of vaporization from the vapor pressure curve
and molar volumes.
First, we should find the normal boiling point by setting P = 101.3 kPa. That gives
sat
3259.93
ln 101.325   13.9726 
T  212.3
3259.93
T  212.3  136.2 C
13.9726  ln 101.325 
Reassuringly, this agrees with the value given in Table B.1 exactly (to the precision given).
  exp  A    exp  A   
dT dT   T  C   T  C 2  T  C  T  C 2
or, using the numbers for ethylbenzene
dP sat 3259.93P sat

dT T  212.32
For T = 136.2 °C and Psat = 101.325 kPa this gives
dP sat 3259.93  101.325
  2.720 kPa K -1
dT 136.2  212.3 2
ethylbenzene are Tc = 617.2 K, Pc = 36.06 bar,  = 0.303, Zc = 0.263, and Vc = 374 cm3 mol-1.
Updated 18/01/2017 11
0.2857
 409.3 
1 
0.2857
1T
 374  0.263 617.2 
 140.5 cm3 mol-1
Because the reduced pressure is only 1.013/36.06 = 0.0281, we expect that the vapor will not be far from
from the Pitzer correlation:
0.422
B 0  0.083   0.7311
0.66321.6
0.172
B1  0.139   0.8262
0.66324.2
and
0.02809
Z  1   0.7311  0.303  0.8262  0.9584
0.6632
So, V = ZRT/P = 0.9584*83.145*409.3/1.013 = 32198 cm3 mol-1.
H  409.35 K  32058 cm3 mol-1  2.720 kPa K-1  3.569  107 kPa cm3 mol-1  3.569  104 J/mol
So, our final answer is H = 35.7 kJ/mol. This agrees with the value in the table to within a few tenths of
a percent --- essentially perfect agreement.
7th edition Prob. 4.12: Do this for toluene and phenol.
Here, we want to use the Clapeyron equation to find the latent heat of vaporization from the vapor pressure
curve and molar volumes. The Clapeyron equation is:
dP sat
H  T V
dT
We will use it, with the known vapor pressure curve and volume change to compute the enthalpy of
vaporization.
(a) Toluene
First, we should find the normal boiling point by setting Psat = 101.3 kPa. Using the Antoine parameters
for toluene this gives
Updated 18/01/2017 12
3056.96
ln 101.325   13.9320 
T  217.625
3056.96
T  217.625   110.6 C
13.9320  ln 101.325 
Reassuringly, this agrees with the value given in Table B.2 essentially exactly.
  exp  A    exp  A   
dT dT   T  C   T  C 2  T  C  T  C 2
or, using the numbers for toluene
dP sat 3056.96 P sat

dT T  217.652
For T = 110.6 C and Psat = 101.325 kPa this gives
dP sat 3056.96  101.325
  2.875 kPa K -1
dT 110.6  217.65 2
toluene are Tc = 591.8 K, Pc = 41.06 bar,  = 0.262, Zc = 0.264, and Vc = 316 cm3 mol-1.
0.2857
 383.8 
1 
0.2857
1T
 316  0.264 591.8 
 117.7 cm3 mol-1
0.422
B 0  0.083   0.7608
0.64851.6
0.172
B1  0.139   0.9215
0.64854.2
and
0.0247
Z  1   0.7608  0.262  0.9215 0.9618
0.6485
So, V = ZRT/P = 0.9618*83.145*383.8/1.013 = 30297 cm mol .
3 -1
Updated 18/01/2017 13
H  383.8 K  30180 cm3 mol-1  2.875 kPa K-1  3.330 107 kPa cm3 mol-1  3.330 104 J/mol
So, our final answer is H = 33.3 kJ/mol. This agrees with the value in table B.2 to within about 0.4%,
which is about the precision of our calculations --- essentially exact agreement.
(b) Now, we repeat the whole thing for phenol --- just for practice:
First, we should find the normal boiling point by setting Psat = 101.3 kPa. Using the Antoine parameters
for phenol, this gives
3507.8
ln 101.325   14.4387 
T  175.4
3507.8
T  175.4   181.8 C
14.4387  ln 101.325 
Reassuringly, this agrees with the value given in Table B.2 essentially exactly.
  exp  A    exp  A   
dT dT   T  C   T  C 2  T  C  T  C 2
or, using the numbers for phenol
dP sat 3507.8P sat

dT T  175.4 2
For T = 181.8 C and Psat = 101.325 kPa this gives
dP sat 3507.8  101.325
  2.786 kPa K -1
dT 181.8  175.4  2
phenol are Tc = 694.3 K, Pc = 61.3 bar,  = 0.444, Zc = 0.243, and Vc = 229 cm3 mol-1.
0.2857
 455 
1 
0.2857
1T  694.3 
 229  0.243  80.7 cm3 mol-1
ideal, even though the reduced temperature is only 455/694.3 = 0.6553. We can get the compressibility
Updated 18/01/2017 14
0.422
B 0  0.083   0.7469
0.65531.6
0.172
B1  0.139   0.8760
0.65534.2
and
0.01653
Z  1   0.7469  0.444  0.8760  0.9713
0.6553
So, V = ZRT/P = 0.9713*83.145*455/1.013 = 36275 cm3 mol-1.
H  455 K  36195 cm3 mol-1  2.786 kPa K-1  4.588 107 kPa cm3 mol-1  4.588 104 J/mol
So, our final answer is H = 45.88 kJ/mol. This agrees with the value in table B.2 to within about 0.7%,
which is about the precision of our calculations --- essentially exact agreement.

Using the equation above, solve for the pressure
Differentiate the above equation and determine dP/dT
Using the Clapeyron equation, solve for V
Then using Eq. 3.37, Solve for B
Updated 18/01/2017 15
To find the total heat exchanger duty, we must consider three process steps: (1) heating of the subcooled
liquid from 300 K to its saturation temperature at 3 bar, (2) vaporization at the saturation temperature, and
(3) heating of the vapor from the saturation temperature to 500 K.
For the first step, we do a heat capacity integral from 300 K to 368.0 K, using the liquid phase heat
capacity:
T2
1 1 
 R dT  AT  T   2 T   
Cp B C 3
ICPH T0,T;A,B,C,D   0
2
 T02  T  T03  D   
T1
3  T T0 
C (1/K2) D (K2) ICPH (K) H (J/mol)

ig
T0(K) T (K) A B (1/K)
300 368.00 13.431 -5.13E-02 1.31E-04 0.00E+00 746.8 6209.3
For the second step, we need the heat of vaporization at 3 bar and 368.0 K. In table B.2, we find the heat
of vaporization at the normal boiling point (337.9 K) is 35.21 kJ/mol. To find the heat of vaporization at
368 K, we can apply the Watson equation (p. 134 of SVNA). This gives:
 1.092(ln Pc - 1.013) 
H 2 = RTn  
 0.930 - Tr 
 
 1.092(ln(80.97 bar) - 1.013) 
H 2 = 8.314 J·mol1·K 1 × 337.9 K ×  
 368 K 
0.930 -
 512.6 K 
H 2 = 48905.00 J·mol1
Finally, for the third step, we have:

T2
1 1 
 R dT  AT  T   2 T   
Cp B C 3
2
 T02  T  T03  D   
T1
3  T T0 

ig
T0(K) T (K) A B (1/K)
368 500.00 2.211 1.22E-02 -3.45E-06 0.00E+00 905.2 7526.6
Comparing these, we see that the vaporization step has the largest contribution to the overall heat
requirement. Adding them gives Q = H = 62.64 kJ/mol/. If the total methanol flow is 100 kmol/hr =
27.78 mol/s, then the total heat exchanger duty is 62.64*27.78 = 1740.13 kW.
4.16. (New)
Need to gather several things for this proble, the boiling point, the latent heat of vaporization, and the heat
capacities for each compound. Using the equation
Updated 18/01/2017 16
And solving it for Tfinal.
(a) Methanol --- Tboiling = 337.85 K , Cp,liq = 81.46 J/mol K , Cp,vap = 46.11 J/mol K , ΔH latent = 35210 J/mol
So for the Liquid:
Now plugging into the first equation and solving for Tfinal gives:
(b) Ethanol --- Tboiling = 351.4 K , Cp,liq = 111.77 J/mol K , Cp,vap = 74.39 J/mol K , ΔH latent = 38560 J/mol
So for the Liquid:
(c) Benzene --- Tboiling = 353.15 K , Cp,liq = 134.33 J/mol K , Cp,vap = 85.29 J/mol K , ΔH latent = 30720 J/mol
So for the Liquid:
(d) Toluene --- Tboiling = 383.75 K , Cp,liq = 154.73 J/mol K , Cp,vap = 107.43 J/mol K , ΔH latent = 33180 J/mol
So for the Liquid:
(e) Water --- Tboiling = 373.15 K , Cp,liq = 75.40 J/mol K , Cp,vap = 33.57 J/mol K , ΔH latent = 40660 J/mol
So for the Liquid:
Updated 18/01/2017 17
Estimate ΔHv using Riedel equation (4.13) and Watson correction (4.14)
Assume the throttling process is adiabatic and isenthalpic.

In each case, we can look up the heat of formation of the compound as a gas in table C.4, where we find
Hf,(acetylene(g)) = 227480 J mol-1, Hf(1,3-butadiene(g)) = 109240 J mol-1, Hf(ethylbenzene(g)) =
29920 J mol , Hf,(n-hexane(g)) = -166920 J mol , Hf(styrene(g)) = 147360 J mol . The heat of formation
-1 -1 -1
of the liquid is equal to the heat of formation of the gas minus the heat of vaporization at 25C. If we only
know the critical properties and normal boiling point of each species, we could estimate this by first using
equation 4.12 to estimate the heat of vaporization at the normal boiling point of each species, and then using
equation 4.13 to estimate the heat of vaporization at 25C. We could, if we like, combine the equations to
get
0.38 0.38
 1  Tr (25 C)   1.092  ln Pc  1.013  1  Tr (25 C) 
H 25 C  H n    RTn   
 1  Tr   0.930  T  1  Tr 
 n   rn  n 
This is getting a bit cumbersome to type into the old calculator, so let's evaluate it in a spreadsheet. Doing
so gives:
Species Tc Pc Tn Trn Tr25C n 25C f

(g) f
(l)
(K) (bar) (K) (J mol ) -1
(J mol ) -1
(J mol )-1
(J mol-1)
acetylene 308.3 61.39 189.4 0.6143 0.9671 16911 6638 227480 220842
1,3-butadiene 425.2 42.77 268.7 0.6319 0.7012 22450 20740 109240 88500
Ethylbenzene 617.2 36.06 409.4 0.6633 0.4831 35852 42196 29920 -12276
Updated 18/01/2017 18
n-hexane 507.6 30.25 341.9 0.6736 0.5874 29010 31712 -166920 -198632
Styrene 636 38.4 418.3 0.6577 0.4688 36753 43434 147360 103926
In the final column above, we have subtracted the latent heat of vaporization at 25 C from the heat of
formation of each species in the gas phase to get the heat of formation of each species in the liquid phase.
4.19 (7 edition Prob. 4.17)

th
1st law: dQ = dU dW = CV dT + P dV (A)
Ideal gas: P V = R T and P dV + V dP = R dT
Whence V dP = R dT P dV (B)
Since P V = const then P V 1

dV = V dP
from which V dP = P dV
Combines with (B) to yield:
Combines with (A) to give:
Which reduces to:
Or
Updated 18/01/2017 19
Since CP is linear in T, the mean heat capacity is the value of

CP at the arithmetic mean temperature. Thus
With , and integrating (C):

The heat of combustion of 6 CH3OH(g) is the heat of reaction for
6 CH3OH(g) + 9 O2(g)  6 CO2(g) + 12 H2O(g)
This is given by Hrxn = 6*Hf(CO2(g) ) + 12*Hf(H2O(g)) - 6*Hf(CH3OH(g) ) = 6*(-393.51) + 12*(-
241.82) -6*(-200.66) = -4059 kJ mol-1.
The heat of combustion of C6H12(g) (assumed to be 1-hexene, though it doesn't really say and there are many
other possible C6H12 isomers) is given by the heat of reaction for
C6H12(g) + 9 O2  6 CO2(g) + 6 H2O(g)
This is given by Hrxn = 6*Hf(CO2(g) ) +6*Hf(H2O(g)) - Hf(C6H12(g) ) = 6*(-393.51) + 6*(-241.82) -
(-41.95) = -3770 kJ mol-1.
The difference between these two heats of combustion is the heat of reaction for the condensation reaction
given in the problem statement. That is, subtracting the second combustion reaction above from the first
gives
6 CH3OH(g)  C6H12(g) + 6 H2O(g)
For which the heat of reaction is -4059 - (-3770) = -289 kJ/mol.
The heat of combustion of ethylene at 25C (with water vapor product) is the heat of reaction for
C2H4(g) +3 O2(g)  2 CO2(g) + 2 H2O(g)
This is given by Hrxn = 2*Hf(CO2(g) ) + 2*Hf(H2O(g)) - Hf(C2H4(g) ) = 2*(-393.51) + 2*(-241.82) -
(52.51) = -1323 kJ mol-1 = -1.323106 J mol-1. The only difference in each case is how much excess O2 and
N2 have to be heated up by the heat released by reaction.
(a) The products (per mole of ethylene burned) will be 2 moles of CO2 + 2 moles of H2O + 3*(79/21) =
11.3 moles of N2 that was included with the 3 moles of O2. So, we integrate the total heat capacity of
Updated 18/01/2017 20
this mixture from 298 K to some final temperature and vary the final temperature until we get H/R =
1.32310 J mol /8.314 J mol K = 159120 K. Doing so, using our handy-dandy heat capacity
6 -1 -1 -1
integrating spreadsheet gives 2533 K.

(b) Similarly, here the products are be 2 moles of CO2 + 2 moles of H2O + 0.25*3 = 0.75 moles of O2 +
3*1.25*(79/21) = 14.1 moles of N2, and integrating the heat capacity of this mixture to get get H/R =
159120 K gives a final temperature of 2198 K.
(c) and (d) are the same as (a) and (b), but with different numbers that lead to final temperatures of 1951
and 1609 K, respectively
(e) Here, we can add the heat required to heat the air from 298K to 773K to the heat of reaction. We can
imagine a path in which we cool the air from 773K to 298K (removing heat H1 = 309424 J per mol
C2H4 burned), carry out the reaction at 298K (releasing the standard heat of reaction, Hrxn = -1.32310 )
6
and then heat the products with both the heat removed to cool the air to 298K and the heat of reaction
(Htot = 1.66310 J per mol C2H4 burned), so the total Htot /R is 196330 K. Both the heat removed to
6
cool the air from 773 to 298 K and the heat required to heat the reaction products to the final temperature
are again computed using the heat capacity integrating spreadsheet. This gives a final temperature of
2282 K. To download the spreadsheet I used to solve this problem, click here.
NOTE: A problem with this homework problem is that several of the final temperatures are above 2000 K,
whereas the heat capacity expressions used (from table C.1 in the book) are only valid up to 2000
K. So, the results for parts (a), (b), and (e) are probably all incorrect (they are the correct answers
to the homework problem, but probably are not good values for the actual adiabaic flame
temperature of ethylene).
C2H4 + 3O2 = 2CO2 + 2H2O(g)
ΔH298= [2⋅(−241818) + 2⋅(−393509) − 52510] = 1323164 J/mol
Parts (a) - (d) can be worked exactly as Example 4.7. However, with
Mathcad capable of doing the iteration, it is simpler to proceed differently.
Index the product species with the numbers:

1 = oxygen
2 = carbon dioxide
3 = water (g)
Updated 18/01/2017 21
4 = nitrogen
(a) For the product species, no excess air:
For the products
The integral is given by Eq. (4.8). Moreover, by an energy balance,
298
+ P
=0
Given
Solving for
Parts (b), (c), and (d) are worked the same way, the only change being in the
numbers of moles of products.
(b) nO2 = 0.75 nN2 = 14.107 T = 2198.6⋅K Ans.
(c) nO2 = 1.5 nN2 = 16.929 T = 1950.9⋅K Ans.
(d) nO2 = 3.0 nN2 = 22.571 T = 1609.2⋅K Ans.
(e) 50% xs air preheated to 500 degC. For this process,
ΔHair + ΔH298 + ΔHP = 0
ΔHair = MCPH⋅(298.15 − 773.15)
For one mole of air:
MCPH (773.15 ,298.15, 3.355, 0.575⋅10−3, 0.0, −0.016⋅105) = 3.65606
For 4.5/0.21 = 21.429 moles of air:

Updated 18/01/2017 22
ΔHair = 21.429⋅8.314⋅3.65606⋅(298.15 − 773.15) = -309399 L/mol
The energy balance here gives: ΔH298 + ΔHair + ΔHP = 0
Given
Solving for
(f)theoretical amount of pure oxygen,
ΔH298 + ΔHP = 0
1323164 J/mol + ΔHP = 0
Starting with a guess and solving iteratively yields:
4.22 (similar to 7th edition Prob. 4.20)
4.22
(a) the heat of combustion of methane gas in the heat of reaction for
CH4 + + 2 O2 (g)  CO2 (g) + 2 H2O (l)
Updated 18/01/2017 23
This is given by Hrxn = *Hf(CO2(g) ) + 2*Hf(H2O(l)) - Hf(CH4(g)) = 1*( -393.51) + 2*(-285.83)-(-

74.520) = -890.65 kJ mol .
-1
(b) The heat of combustion of ethane gas is the heat of reaction for
2 C2H6 + + 7 O2 (g) 4 CO2 (g) + 6 H2O (l)

This is given by Hrxn = 4*Hf(CO2(g) ) + 6*Hf(H2O(l)) --- 2*Hf (C2H6 (g))
= 4*( -393.51) + 6*(-285.83)-2*(-83.820) = -3121.38 kJ mol-1.
(c) The heat of combustion of ethylene gas is the heat of reaction for
C2H4 + + 3 O2 (g) 2 CO2 (g) + 2 H2O (l)

This is given by Hrxn = 2*Hf(CO2(g) ) + 2*Hf(H2O(l)) --- *Hf (C2H6 (g))
= 2*( -393.51) + 2*(-285.83)-(-52.510) = -1306.17 kJ mol-1.
(d) The heat of combustion of propane gas is the heat of reaction for
C3H8 + + 5 O2 (g) 3 CO2 (g) + 4 H2O (l)

= 3*( -393.51) + 4*(-285.83)-(-104.680) = -2219.47 kJ mol-1.
(e) The heat of combustion of propylene, gas is the heat of reaction for
2 C3H6 + + 9 O2 (g) 6 CO2 (g) + 6 H2O (l)

This is given by Hrxn = 6*Hf(CO2(g) ) + 6*Hf(H2O(l)) --- 2*Hf (C3H6 (g))
= 6*( -393.51) + 6*(-285.83)-2*(-19.710) = -4036.62 kJ mol-1.
(f) The heat of combustion of n-butane , gas is the heat of reaction for
C4H10 + + 13/2 O2 (g) 4 CO2 (g) + 5 H2O (l)

= 4*( -393.51) + 5*(-285.83)-(-125.790) = -2877.4 kJ mol-1.
(g) The heat of combustion of 1-butene, gas is the heat of reaction for
C4H8 + + 6 O2 (g) 4 CO2 (g) + 4 H2O (l)
Updated 18/01/2017 24
= 4*( -393.51) + 4*(-285.83)-(-0.540) = -2716.82 kJ mol-1.
(h) The heat of combustion of ethylene oxide, gas is the heat of reaction for
C4H8 + + 6 O2 (g) 4 CO2 (g) + 4 H2O (l)

= 4*( -393.51) + 4*(-285.83)-(-0.540) = -2716.82 kJ mol-1.
(i) The heat of combustion of acetaldehyde gas is the heat of reaction for
CH3CHO+ 2.5 O2 (g) 2 CO2 (g) + 2 H2O (l)

This is given by Hrxn = 2*Hf(CO2(g) ) + 2*Hf(H2O(l)) --- *Hf (CH3CHO (g))
= 2*( -393.51) + 2*(-285.83)-(-166.190) = -1192.49 kJ mol-1.
(j) The heat of combustion of methanol gas is the heat of reaction for
2 CH3OH+ 3 O2 (g) 2 CO2 (g) + 4 H2O (l)

This is given by Hrxn = 2*Hf(CO2(g) ) + 4*Hf(H2O(l)) --- 2*Hf (CH3OH (g))
= 2*( -393.51) + 4*(-285.83)-2*(-200.660) = -1529.02 kJ mol .

-1
(k) The heat of combustion of ethanol gas is the heat of reaction for
C2H6 O+ 6 O2 (g) 2 CO2 (g) + 3 H2O (l)

This is given by Hrxn = 2*Hf(CO2(g) ) + 3*Hf(H2O(l)) --- *Hf (C2H6O (g))
= 2*( -393.51) + 4*(-285.83)-(-235.100) = -1695.24 kJ mol-1.

(a) Hrxn = 2*Hf(NH3(g) ) - Hf(N2(g)) --- 3*Hf(H2(g)) = 2*(-46.110) ---0-0 = -92.22 kJ mol-1.
(b) Hrxn = 4*Hf(NO(g)) + 6*Hf(H2O(g)) --- 4*Hf(NH3(g) --- 5*Hf(O2(g))
Hrxn = 4*(90.25) + 6*(-241.82) --- 4*(-46.110) --- 5*(0)= -905.5 kJ mol-1.
(c) Hrxn = 2*Hf(HNO3(l)) + Hf(NO(g)) --- 3*Hf(NO2(g)) - Hf(H2O(l))
Hrxn = 2*(-174.1) + (90.25) --- 3*(33.18) - (-285.830) = -71.66 kJ mol-1.
(d) Hrxn = Hf(CaO(s) ) + Hf(C2H2(g)) --- Hf(CaC2(s)) - Hf(H2O(l))
Hrxn = -635.090 + 227.480 + 59.800 + 285.830 = -61.98 kJ mol-1.
(e) Hrxn = 2*Hf(NaOH(s)) + Hf(H2(g)) - 2*Hf(Na(s)) --- 2*Hf(H2O(g))
Updated 18/01/2017 25
Hrxn = 2*(-425.609) + 0 --- 2*(0) --- 2*(-241.818)= -367.6 kJ mol-1.

(f) Hrxn = 7*Hf(N2(g)) + 12*Hf(H2O(g)) --- 6*Hf(NO2(g)) --- 8*Hf(NH3(g))
Hrxn = 7*(0) + 12*(-241.818) --- 6*(33.18) --- 8*(-46.110) = -2732 kJ mol-1.
(g) Hrxn = Hf )
2 2
- Hf(C2H4(g)) --- ½ Hf(O2(g))
Hrxn = -52630 --- 52510 --- 0 = -105140 J mol
-1
(h) Hrxn = Hf )

2 2
- Hf(C2H2(g)) --- Hf(H2O(g))
Hrxn = -52630 --- 227480 --- -241818 = -38292 J mol-1
(i) Hrxn = Hf(CO2(g)) + 4*Hf(H2(g)) - Hf(CH4(g)) --- 2*Hf(H2O(g))
Hrxn = - 4*(92307)+ 2*(-241818) = -1.144 * 105 J mol-1
(j) Hrxn = Hf(CH3OH(g)) + Hf(H2O(g)) - Hf(CO2(g)) --- 3*Hf(H2(g))
Hrxn = -200660 - 241818 - -393509 --- 3*0 = -48969 J mol
-1
(k) Hrxn = Hf(HCHO(g)) + Hf(H2O(g)) - Hf(CH3OH(g)) --- ½ *Hf(O2(g))

Hrxn = -108570 - 241818 - -200660 --- ½*0 = -149728 J mol
-1
(l) Hrxn = 2*Hf(H2O(g)) + 2*Hf(SO2(g)) - 2*Hf(H2S(g)) --- 3 *Hf(O2(g))

Hrxn = 2*-241818 -2*296830 +2*20630 --- 3*0 = -1036036 J mol-1
(m) Hrxn = 3*Hf(H2(g)) + Hf(SO2(g)) - Hf(H2S(g)) --- 2*Hf(H2O(g))
Hrxn = 3*0 + -296830 + 20630 --- 2*-241818 = 207436 J mol
-1
(n) Hrxn = 2*Hf(NO(g)) - Hf(N2(g)) --- Hf(O2(g))

Hrxn = 2*90250 --- 0 --- 0 = 180500 J mol
-1
(o) Hrxn = Hf(CaO(s)) + Hf(CO2(g)) --- Hf(CaCO3(s))

Hrxn = -635090 --- 393509 + 1206920 =178321 J mol-1
(p) Hrxn =Hf(H2SO4(l)) - Hf(SO3(g)) --- Hf(H2O(l))
Hrxn = -813989 + 395720 + 285830 = -132439 J mol-1
(q) Hrxn = Hf(C2H5OH(l)) - Hf(C2H4(g)) --- Hf(H2O(l))
Hrxn = -277690 --- 52510 + 285830 = -44370 J mol-1
(r) Hrxn = Hf(C2H5OH(g)) - Hf(CH3CHO(g)) --- Hf(H2(g))
Hrxn = -235100 +166190 --- 0 = -68910 J mol-1
(s) Hrxn = Hf(CH3COOH(l)) + Hf(H2O(l)) - Hf(C2H5OH(l)) --- Hf(O2(g))
Hrxn = -484500 -285830 + 277690 --- 0 = -492640 J mol-1
(t) Hrxn = Hf(CH2:CHCH:CH2(g)) + Hf(H2(g)) - Hf(C2H5CH:CH2(g))
Hrxn = 109240 + 0 + 540 = 109780 J mol-1
(u) Hrxn = Hf(CH2:CHCH:CH2(g)) + 2*Hf(H2(g)) - Hf(C4H10(g))
Hrxn = 109240 + 0 + 125790 = 235030 J mol-1
(v) Hrxn = Hf(CH2:CHCH:CH2(g)) + Hf(H2(g)) - Hf(C2H5CH:CH2(g))- Hf(O2(g))-
Hrxn = 109240 +(-241818)-(-540) = -132038 J mol-1
(w) Hrxn = 4*Hf(NH3(g)) -6* Hf(NO(g)) --- 6*Hf(H2O(g))- 5*Hf(N2(g))-
Updated 18/01/2017 26
Hrxn =4(-46110) --- 6(90250) --- 6*(241818) - 0 = -1807968 J mol-1
(x) Hrxn = 2*Hf(HCN(g) ) - Hf(C2H2(g)) = 2*(135.1) - (227.48) = 42.72 kJ mol-1.

(y) Hrxn = Hf(styrene) - Hf(ethylbenzene) = (147.36) - (29.92) = 117.44 kJ mol .
-1
(z) Hrxn = Hf(CO(g)) - Hf(H2O(l)) = (-110.525) - (-285.830) = 175.305 kJ mol-1.

(a) A heat of reaction at a temperature other than standard temperature is given by the heat of reaction at
standard temperature plus the integral of the difference in heat capacity between products and reactants:
 C 
T
H rxn
o
,T  H rxn,298.15 K 
o total
p ,products  C ptotal
,reactants dT
298.15 K
A handy spreadsheet for evaluating the integral was provided in the lecture notes. Putting in the parameters
for the reaction
N2 + 3 H2 3
We have
T
1 1 
IDCPH  T0 ,T; A, B, C, D 
1
R 
C p dT  A T  T0  
B 2
2
T  T02 
C 3
3

T  T03  D   
 T T0 
  
To
T0 (K) T (K) A B (1/K) C (1/K2) D (K2) IDCPH (K)

298.15 873.15 -5.871 4.18E-03 0.00E+00 -6.61E+04 -2113.9
Species Stoichiometric
Name coefficient A B (1/K) C (1/K2) D (K2) n i Ai
N2 -1 3.28 5.93E-04 0.00E+00 4.00E+03 -3.28E+00
H2 -3 3.249 4.22E-04 0.00E+00 8.30E+03 -9.75E+00
NH3 2 3.578 3.02E-03 0.00E+00 -1.86E+04 7.16E+00
Multiplying the result by R gives - Cp. The heat of reaction at 298.15 K
is just twice the heat of formation of ammonia, because this is the formation reaction for ammonia,
written with 2 NH3 H298 = -46110 J/mol *2 = -92.22 kJ/mol. Adding on the
Cp gives H600°C = -109.80 kJ/mol for the reaction as written.
(b) Repeating this for the reaction 4 NH3 + 5 O2 2

O gives
Updated 18/01/2017 27
T
1 1 
IDCPH  T0 ,T; A, B, C, D 
1
R
C p dT  A T  T0  

B 2
2
T  T02 
C 3
3
T  T03  D   
 T T0 
   
To
T0 (K) T (K) A B (1/K) C (1/K2) D (K2) IDCPH (K)

298.15 773.15 1.861 -3.39E-03 0.00E+00 2.66E+05 568.8
Species Stoichiometric
Name coefficient A B (1/K) C (1/K2) D (K2) n i Ai
NH3 -4 3.578 3.02E-03 0.00E+00 -1.86E+04 -1.43E+01
O2 -5 3.639 5.06E-04 0.00E+00 -2.27E+04 -1.82E+01
NO 4 3.387 6.29E-04 0.00E+00 1.40E+03 1.35E+01
H2O 6 3.47 1.45E-03 0.00E+00 1.21E+04 2.08E+01
Multiplying the result by R gives 4.729 kJ/mol for the Cp. The heat of reaction at 298.15 K is
given by:
H298 H298(H2 H298(NO) --- H298(NH3)
H298 = 6*(-241.818) + 4*90.250 --- 4*(-46.11) = -905.47 kJ/mol.
H500°C = -900.74 kJ/mol.
(f) A heat of reaction at a temperature other than standard temperature is given by the heat of reaction at
standard temperature plus the integral of the difference in heat capacity between products and reactants:
 C 
T
H rxn
o
,T  H rxn,298.15 K 
o total
p ,products  C ptotal
,reactants dT
298.15 K
A handy spreadsheet for evaluating this was provided in the lecture notes. Putting in the parameters for the
reaction
6 NO2(g) + 8 NH3(g)  7 N2(g) + 12 H2O (g)
gives:
Reference Temperature Heat of Heat Capacity Heat of T
1 1 1 
 C dT  T  A T  T   2 T   
1 B C 3
Temperature of Interest Reaction at T 0 Integral Reaction at T p 0
2
 T02  T  T03   D    
RT 3  T T0  
T 0 (K) T (K) kJ/mol (dimensionless) kJ/mol To
298.15 923.15 -2732.016 2.037 -2716.380
 1 1 
Heat Capacity Coefficients  H rxn
o
,T   H rxn ,T0  R   A  T  T 0  
o B 2

T  T02  
C 3

T  T 03   D    
Standard Heat  2 3  T T0  
Species Stoichiometric of Formation
2 2
Name coefficient at T 0 (kJ/mol) A B (1/K) C (1/K ) D (K ) niHf,i niAi niBi niCi niDi
NO2 -6 33.18 4.982 1.20E-03 0.00E+00 -7.92E+04 -1.99E+02 -2.99E+01 -7.17E-03 0.00E+00 4.75E+05
NH3 -8 -46.11 3.578 3.02E-03 0.00E+00 -1.86E+04 3.69E+02 -2.86E+01 -2.42E-02 0.00E+00 1.49E+05
N2 7 0 3.28 5.93E-04 0.00E+00 4.00E+03 0.00E+00 2.30E+01 4.15E-03 0.00E+00 2.80E+04
H2O 12 -241.818 3.47 1.45E-03 0.00E+00 1.21E+04 -2.90E+03 4.16E+01 1.74E-02 0.00E+00 1.45E+05
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
A B (1/K) C (1/K ) D (K )
2 2
6.084 -9.78E-03 0.00E+00 7.97E+05

Note: Light blue fields are inputs, pink fields are the final output.
Updated 18/01/2017 28
The heat of reaction at 650C is -2716 kJ/mol. This is only slightly different from the heat of reaction at
standard conditions. It just happens that the average heat capacity of the reactants and products is about
the same over this temperature range.
This is a simple application of a combination of Eqs. (4.19) & (4.20) with

evaluated parameters. In each case the value of ΔH0298 is calculated in Pb.
4.23. The values of ΔA, ΔB, ΔC and ΔD are given for all cases except for
Parts (e), (g), (h), (k), and (z) in the preceding table. Those missing are as
follows:
Part No. ΔA 103 ΔB 106 ΔC 10-5 ΔD
e -7.425 20.778 0 3.737
g -3.629 8.816 -4.904 0.114
h -9.987 20.061 -9.296 1.178
k 1.704 -3.997 1.573 0.234
z -3.858 -1.042 0.18 0.919
4.26 (New)
Use table C.5 to find the standard enthalpies.
(a)Reactants = -1262.2 kJ/mol + -3627.9 kJ/mol = -4890.1 kJ/mol
Products = -2274.6 kJ/mol + -2638.5 kJ/mol = -4913.1 kJ/mol
Products --- Reactants = -4913.1 J/mol --- (-4881.4) J/mol = -23 J/mol
(b) Reactants = -2274.6 kJ/mol
Products = -2265.9kJ/mol
Products --- Reactants = 8.7 kJ/mol
(c) Reactants = -5893.8 kJ/mol
Products = -5956.8 kJ/mol
Products --- Reactants = -63 kJ/mol
(d) Reactants = -9144.4 J/mol
Products = -9083.66J/mol
Products --- Reactants = 60.74 kJ/mol
(e) Reactants = -9144.4 J/mol
Products = -9200.66 J/mol
Products --- Reactants = -56.26 kJ/mol
(f) Reactants = -9144.4 kJ/mol
Updated 18/01/2017 29

Products --- Reactants = -87.26 J/mol
(g) Reactants = -75.5 kJ/mol
(h) Reactants = -3941.1 kJ/mol
(i) Reactants = -7957 kJ/mol
Products --- Reactants = --441.42 kJ/mol
(j) Reactants = -9141.6 kJ/mol
(k) Reactants = -9137.4 kJ/mol
(l) Reactants = -4703.8 kJ/mol
Products --- Reactants = - 3.4 kJ/mol
4.27 (New)
First determine how many moles of ethanol we have, MWetoh = 46.068 g/mol. Moles of EtOH = 10 g/
46.068 g/mol = 0.217 mol.
Now, Balance the equation

C2H5OH + NAD+ → C2H4O + NADH + H
   
H f 298 = (-212.2 J·mol1 ) + (-31.9 J·mol1 ) + 0 J·mol1 - (-288.3 J·mol1 ) + 0 J·mol1 = 44.2 J·mol1
H = 0.217 mol × H f 298 = 0.217 mol × 44.2 J·mol1 = 9.59 J
For the second part, write the equation
Updated 18/01/2017 30
C2H5OH + NAD+ → (2CO2 + 2H2O) + NADH + H
  
H f 298 = 2(-393509 J·mol1 ) + 2(-285830 J·mol 1 ) + (-31.9 J·mol1 ) + 0 J·mol1 - -288.3 J·mol 1 + 0 J·mol1 
H = -0.217 mol × H f 298 = 0.217 mol × (-1358421.6 J·mol1 ) = -294777.4872 J
This reaction gives off heat as it proceeds in the reaction.

T = 288.71 K P= 1 atm
The higher heating value is the negative of the heat of combustion with water as liquid
product.
Calculate methane standard heat of combustion with water as liquid product:
CH4 + 2O2  CO2 +2H2O
Standard Heats of Formation:
⋅ − − ⋅
Assuming methane is an ideal gas at standard conditions:

Calculate methane standard heat of combustion with water as liquid product
Standard Heats of Formation:CH4 + 2O2 --> CO2 +2H2O
Updated 18/01/2017 31
⋅ − − ⋅
Calculate ethane standard heat of combustion with water as liquid product:
Standard Heats of Formation:C2H6 + 7/2O2 --> 2CO2 +3H2O
⋅ ⋅ − − ⋅
Calculate propane standard heat of combustion with water as liquid product
Standard Heats of Formation:C3H8 + 5O2 --> 3CO2 +4H2O
⋅ ⋅ − − ⋅
Calculate the standard heat of combustion for the mixtures

(a)
⋅ ⋅ ⋅
(b)
⋅ ⋅ ⋅
(c)
⋅ ⋅ ⋅
Gas b) has the highest standard heat of combustion.

The heat of combustion is defined as the heat of reaction for
CO2(g) + 2 H2O (l) + N2(g)  (NH2)2CO(s) + 3/2 O2(g)
Because the number given for the heat of combustion is positive, we know that it is for formation of urea
plus oxygen from the combustion products (the reverse of the combustion reaction).
Updated 18/01/2017 32
So, the heat of combustion at 25C is

Hcomb(298) = ½*Hf(O2(g)) + Hf((NH2)2CO(s)) - Hf(CO2(g)) - 2*Hf(H2O(l)) - Hf(N2(g))
We know all of the quantities in the above equation except the heat of formation of urea. So, we can put
the numbers in and solve for
Hf((NH2)2CO(s)) = Hf(CO2(g)) + 2*Hf(H2O(l)) + Hf(N2(g)) ---1.5*Hf(O2(g)) + Hcomb(298)
Hf((NH2)2CO(s)) = -393.509 + 2*(-285.83) + 0 --- 1.5*0 + 631.66 = -333.5 kJ/mol.

(a) There is nothing profound here. If we compute the heat of combustion with water as a liquid product,
then the value we get is higher (larger in absolute value) than if we compute it with water as a vapor
product. They differ by the value of the heat of vaporization of water at 25C, which is 44012 J mol-1.
(b) The heat of combustion for methane with liquid water as the product is the heat of reaction for CH4(g)
+ 3 O2(g)  CO2(g) + 2 H2O(l), which is Hrxn = Hf(CO2(g) ) + 2*Hf(H2O(l)) - Hf(CH4(g) ) = -
393.51 + 2*(-285.83) -(-74.52) = -890.7 kJ mol-1. With water vapor as the product, it is -802.6 kJ/mol.
Heating values for gaseous fuels are more commonly expressed in Btu per standard cubic foot. If we
treat methane as an ideal gas and choose the commonly used 'standard conditions' for natural gas of
60F and 1 atm, then at there will be n/V = P/RT = 1 atm/(0.7302 SCF atm lbmol-1 R-1 * 519.7 R) =
0.00264 lbmol /SCF= 1.195 mol /SCF. Multiplying this by the higher heating value in kJ/mol gives
1.195*-890.7= -1064 kJ/SCF = -1009 Btu/SCF (Perry's handbook lists 1012 Btu ft-3, so we probably
did it right). Multiplying it by the lower heating value gives -909 Btu/SCF. So, the HHV = 1009
Btu/SCF and the LHV = 909 Btu/SCF.
(c) Similarly, the heat of combustion with liquid water product for n-decane is the heat of reaction for
C10H22(l) + 15.5 O2(g) 10 CO2(g) + 11 H2O(l), which is Hrxn = 10*Hf(CO2(g) ) + 11*Hf(H2O(l)) -
Hf(C10H22(l) ) = 10*(-393.51) + 11*(-285.83) -(-249.7) = -6829.5 kJ mol-1. Similarly, the value with
gas phase water product is -6345.4 kJ mol-1. For liquid fuels, the heating value is usually expressed as
Btu per gallon of the liquid. The density of n-decane (from Perry's handbook) is 0.73 g cm , and the
-3
molecular weight is 142.3 g mol-1, so we get HHV = 6829.5 kJ mol-1 / 143 g mol-1 * 0.73 g cm-3 = 34.86
kJ/cm3 * 3785 cm3 gal-1 * 0.9478 Btu kJ-1 = 125000 Btu gal-1. Likewise, the lower heating value is
116000 Btu gal-1.

On the basis of 1 mole of C10H18
(molar mass = 162.27)
Updated 18/01/2017 33
This value is for the constant-volume reaction:
C10H18(l) + 14.5O2(g) = 10CO2(g) + 9H2O(l)
Assuming ideal gases and with symbols representing total properties,
This value is for the constant-V reaction, whereas the STANDARD reaction is at const. P.
However, for ideal gases H = f(T), and for liquids H is a very weak function of P. We
therefore take the above value as the standard value, and for the specified reaction:
C10H18(l) + 14.5O2(g) = 10CO2(g) + 9H2O(l) ΔH
9H2O(l) = 9H2O(g)
___________________________________________________
C10H18(l) + 14.5O2(g) = 10CO2(g) + 9H2O(g)
298
:= + vap
= -6748436 J

FURNACE: Basis is 1 mole of methane burned with 30% excess air.
CH4 + 2O2 = CO2 + 2H2O(g)
Entering:
Total moles of dry gases entering
At 30 degC the vapor pressure of water is 4.241 kPa. Moles of water vapor entering:
Leaving: CO2 -- 1 mol

H2O -- 2.585 mol
O2 -- 2.6 - 2 = 0.6 mol
N2 -- 9.781 mol
Updated 18/01/2017 34
By an energy balance on the furnace:
Q = ΔH = ΔH303 + ΔHP
From Example 4.7: ΔH298 = -802625 J/mol
ΔH303 = ΔH298 + MCPH * R * (T – T0) = -802279 J/mol
For evaluation of ΔHP we number species as above.
The TOTAL value for MCPH of the product stream:
ΔHP = R⋅MCPH(303.15K,1773.15K,A,B,C,D)⋅(1773.15 − 303.15)K

ΔHP = 731982 kJ/mol
Q =ΔHP + ΔH303 = −70.30 kJ
HEAT EXCHANGER: Flue gases cool from 1500 C to 50 C. The partial pressure of the water
in the flue gases leaving the furnace (in kPa) is
The vapor pressure of water at 50 degC (exit of heat exchanger) is 12.34 kPa, and water
must condense to lower its partial pressure to this value.
Moles of dry flue gases:
Moles of water vapor leaving the heat exchanger:
Moles of water condensing:
Latent heat of water at 50 C in J/mol:

Updated 18/01/2017 35
Sensible heat of cooling the flue gases to 50 degC with all the water as
vapor (we assumed condensation at 50 degC):
⋅ ⋅ ⋅ ⋅ − − ⋅

4NH3(g) + 5O2(g) = 4NO(g) + 6H2O(g)
BASIS: 4 moles ammonia entering reactor
Moles O2 entering = (5)(1.3) = 6.5
Moles N2 entering = (6.5)(79/21) = 24.45
Moles NH3 reacting = moles NO formed = (4)(0.8) = 3.2
Moles O2 reacting = (5)(0.8) = 4.0
Moles water formed = (6)(0.8) = 4.8
ENERGY BALANCE:
ΔH = ΔHR + ΔH298 + ΔHP = 0
REACTANTS: 1=NH3; 2=O2; 3=N2
TOTAL mean heat capacity of reactant stream:

⋅ ⋅ −
The result of Pb. 4.23(b) is used to get
)= -724374.4 J/mol
Products
Updated 18/01/2017 36
Given

The enthalpy balance for this steady-state flow process in which no non-flow work is done simply gives Q
= H, where H is the enthalpy of the ethanol stream leaving the reactor minus the enthalpy of the ethylene
and water entering the reactor. To compute the enthalpy change, we can use an imaginary 2-step path in
which we first cool the ethane and water from 320C to 25C, and then carry out the reaction. The total
enthalpy change will be the sum of the entropy change for the two steps:

298.15 K
H  C pfeed dT  H rxn
o
,298.15 K
593.15 K
The choice of doing the heat capacity integral first (from 320 to 25C) is particularly convenient because
the final temperature happens to be the standard temperature for heats of formation. In general, if we have
reactants and products at different temperatures, we would have to do two heat capacity integrals --- one
from the feed temperature to 298.15 K and one from 298.15 K back to the product temperature.
The heat of reaction is

Hrxn = Hf(C2H5OH(l)) - Hf(H2O(g)) --- Hf(C2H4(g))
Hrxn = -277690 --- (-241818) --- (52510) = -88382 J/mol
We can use the handy spreadsheet from the lecture notes to evaluate the heat capacity integral:

593.15 298.15 4.894 1.58E-02 -4.39E-06 1.21E+04 -3.28E+03
T2
1
    
Cp B 2 C 3 1
dT A T2 T1 
ICPH  T2 T12 T2 T13 D 
R 2 3 T2 T1
T1
Updated 18/01/2017 37
Where for A, B, C, and D, we use the sum of the values for water and ethylene. Multiplying this by R gives

298.15 K
C pfeed dT  8.314*(3820)  27270 J mol-1
593.15 K
Thus, the total heat load of the process is
Q = H = -88380 --- 27270 = -115560 J/mol = -115.6 kJ/mol
We must remove 115.6 kJ of heat from the reactor for each mole of ethanol produced.

Let x1 be the extent of the first reaction and x2 be the extent of the second reaction, defined so that they are
extensive extents of reaction with units of moles, so that the number of moles of each species coming out
of the reactor are
nCH4 = nCH4,o - x1
nH2O = nH2O,o - x1 - x2
nCO = x1 - x2
nH2 = 3x1 + x2
and nCO2 = x2
Given the reactor outlet composition in mole fractions, and doing the problem on a 'per mole of outlet gas'
basis, the number of moles of each species coming out is just the given mole fractions, so we have
nCH4 = nCH4,o - x1 = 0
nH2O = nH2O,o - x1 - x2 = 0.1725
nCO = x1 - x2 = 0.1725
nH2 = 3x1 + x2 = 0.6275
and nCO2 = x2 = 0.0275
Note that because the four given mole fractions sum to 1, the mole fraction of CH4 in the outlet (not
explicitly given) is zero. Above, we have 5 equations in 4 unknowns (x1, x2, nCH4,o, and nH2O,o), but
fortunately they are consistent. From them, we get x2 = 0.0275, x1 = 0.2000, nCH4,o = 0.2000, and nH2O,o =
0.4000. That is, for each mole of the product stream, 0.4 moles of H2O and 0.2 moles of CH4 are fed to
the reactor, and 0.2 moles of reaction 1 occur and 0.0275 moles of reaction 2 occur.
H = Q. The heat input is
equal to the enthalpy difference between the product stream and the reactant stream. This can be
computed as the sum of three steps:
(1) The change in enthalpy when 0.4 mol H2O and 0.2 mol CH4 are cooled from 500 ºC to 25 º C
Updated 18/01/2017 38
(2) 0.2 times the standard heat of reaction at 25ºC for CH4 + H2 2
plus 0.0275 times the
standard heat of reaction for CO + H2 2
+ H2
(3) The change in enthalpy when a mixture of 0.0275 mol CO2, 0.1725 mol CO, 0.1725 mol H2O, and
0.6275 mol H2 is heated from 25 ºC to 850 ºC.
For step (1), we can use one of our handy spreadsheets. A version adapted for gas mixtures is shown
below:
T
1 1 
IDCPH T0,T; A,B,C,D  
1
RC p dT  A T  T0   
B 2
2

T  T02 
C 3
3
 
T  T03  D   
 T T0 
To
T 0 (K) T (K) ΔA ΔB (1/K) ΔC (1/K2) ΔD (K2) IDCPH (K) ΔH (J)

773.15 298.15 1.7284 2.40E-03 -4.33E-07 4.84E+03 -1377.787 -11455
Species Amount
Name (moles) A B (1/K) C (1/K2) D (K2) niAi niBi niCi niDi
CH4 0.2 1.702 9.08E-03 -2.16E-06 0.00E+00 3.40E-01 1.82E-03 -4.33E-07 0.00E+00
H2O 0.4 3.47 1.45E-03 0.00E+00 1.21E+04 1.39E+00 5.80E-04 0.00E+00 4.84E+03
CO 0 3.376 5.57E-04 0.00E+00 -3.10E+03 0.00E+00 0.00E+00 0.00E+00 0.00E+00
H2 0 3.249 4.22E-04 0.00E+00 8.30E+03 0.00E+00 0.00E+00 0.00E+00 0.00E+00
CO2 0 5.547 1.05E-03 0.00E+00 -1.16E+05 0.00E+00 0.00E+00 0.00E+00 0.00E+00
For step (3), we do the same thing, but with the composition of the product stream and the appropriate
temperatures:
T
1 1 
IDCPH T0,T; A,B,C,D  
1
RC p dT  A T  T0   
B 2
2

T  T02 
C 3
3
 
T  T03  D   
 T T0 
To
T 0 (K) T (K) ΔA ΔB (1/K) ΔC (1/K2) ΔD (K2) IDCPH (K) ΔH (J)

298.15 1123.15 3.372225 6.40E-04 0.00E+00 3.58E+03 3165.980 26322
Species Amount
Name (moles) A B (1/K) C (1/K2) D (K2) niAi niBi niCi niDi
CH4 0 1.702 9.08E-03 -2.16E-06 0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
H2O 0.1725 3.47 1.45E-03 0.00E+00 1.21E+04 5.99E-01 2.50E-04 0.00E+00 2.09E+03
CO 0.1725 3.376 5.57E-04 0.00E+00 -3.10E+03 5.82E-01 9.61E-05 0.00E+00 -5.35E+02
H2 0.6275 3.249 4.22E-04 0.00E+00 8.30E+03 2.04E+00 2.65E-04 0.00E+00 5.21E+03
CO2 0.0275 5.547 1.05E-03 0.00E+00 -1.16E+05 1.53E-01 2.87E-05 0.00E+00 -3.18E+03
For step (2), the relevant heats of formation are:
Reaction 1: Reaction 2:
Standard Heat Standard Heat
Species Stoichiometric of Formation Species Stoichiometric of Formation
Name coefficient at T 0 (kJ/mol) Name coefficient at T 0 (kJ/mol)
CH4 -1 -74.52 CO -1 -110.53
H2O -1 -241.818 H2O -1 -241.818
CO 1 -110.53 CO2 1 -393.509
H2 3 0 H2 1 0
Ho298(rxn Ho298(rxn 2) = -41161 J/mol
H = 0.2*205808 + 0.0257*-41161 = 40030 J.
Thus, the total for the three steps is -11455 + 40030 + 26322 = 54897 J.

Updated 18/01/2017 39
le of fuel (0.75 mol of methane and 0.25 mol of ethane). Because we use excess
air, we can safely assume complete combustion of the fuel to give CO2 and water. So, we have two
combustion reactions:
CH4 + 2 O2  CO2 + 2 H2O
C2H6 + 7/2 O2  2CO2 + 3 H2O
Burning the 0.75 mol of CH4 requires 2*0.75 = 1.5 mol of O2, and burning the 0.25 mol of C2H6 requires
0.25*7/2 = 7/8 = 0.875 mol O2. So, the total O2 required for stoichiometric combustion of the fuel is 2.375
mol O2 per mole of fuel. If we use 80% excess air, that means we have 1.8 times this much O2, and the O2
feed rate is 1.8*2.375 = 4.275 mol O2 per mole of fuel. Because we are using air, we get 79/21 moles of
N2 for every mole of O2, and therefore the N2 feed rate is 79/21*4.275 = 16.08 mol N2 per mole of fuel. So,
the feed to the furnace is (per mole of fuel)
0.75 mol CH4

0.25 mol C2H6
4.275 mol O2
16.08 mol N2
The flue gas has the same amount of N2 as the feed, but all of the CH4 and C2H6 (and some of the O2) have
been converted to CO2 and H2O. The 0.75 mol of CH4 produces 0.75 mol of CO2 and 1.5 mol of H2O. The
0.25 mol C2H6 produces 0.5 mol CO2 and 0.75 mol H2O. We already figured out that the stoichiometric O2
(the amount used up in burning the fuel) is 2.375 mol O2, so we have 4.275 --- 2.375 = 1.9 mol O2 remaining
in the flue gas (this is the 80% excess O2). So the flue gas leaving the furnace is (per mole of fuel)
1.9 mol O2
1.25 mol CO2
2.25 mol H2O
16.08 mol N2
The energy balance is simply Q = H, where H is the enthalpy change between the feed stream and the
flue gas stream and Q is specified as -8105 kJ per kgmol of fuel (or J per mol of fuel). We can compute
the total H from feed to flue gas using a hypothetical three-step process in which we cool the feed from
30C to 25C, then react it at 25C, then heat it to the flue gas outlet temperature (which we are supposed
to find). So, we have

298.15 K

T flue
H  C pfeed dT  H rxn
o
,298.15 K  C pflue dT  Q
303.15 K 298.15 K
Updated 18/01/2017 40
We know Q, and we can compute the first heat capacity integral and the standard enthalpy of reaction, then
we can find the flue gas temperature (by trial and error) that satisfies the above energy balance. For the
integral of the feed heat capacity, we can use the same spreadsheet as always:
T1 (K) T2 (K) A B (1/K) C (1/K ) D (K ) ICPH (K)
2 2
303.15 298.15 68.70413 0.023316 -3E-06 -32722.5 -3.75E+02
T2
1
    
Cp B 2 C 3 1
dT A T2 T1 
ICPH  T2 T12 T2 T13 D 
R 2 3 T2 T1
T1
CH4 1.702 9.08E-03 -2.16E-06 0

C2H6 1.131 1.92E-02 -5.56E-06 0
O2 3.369 5.06E-04 0 -2.27E+04
N2 3.28 5.93E-04 0 4.00E+03
CO2 5.457 1.05E-03 0 -1.16E+05
H2O 3.47 1.45E-03 0 1.21E+04
For convenience, I have entered the heat capacity coefficients of the individual species, which I then add
up (multiplied by the number of moles of each species) to get the total heat capacity coefficients of the
mixture. Note that I can type in the formula once (for A) and then fill right to get B, C, and D. So, this
gives us

298.15 K
C pfeed dT  375R  3118 J mol-1
303.15 K
The total heat of reaction is 0.75 times the enthalpy of reaction for CH4 + 2 O2  CO2 + 2 H2O, plus 0.25
times the enthalpy of reaction for CH4 + 2 O2  CO2 + 2 H2O, or
Hrxn =0.75*(Hf(CO2) +2Hf(H2O) --- Hf(CH4)) + 0.25*(2Hf(CO2) +3Hf(H2O) --- Hf(C2H6))
Hrxn =1.25*Hf(CO2) +2.25Hf(H2O) ---0.75Hf(CH4)) --- 0.25Hf(C2H6))
Hrxn =1.25*(-393509)+2.25(-241818) ---0.75(-74520) --- 0.25(-83820) = -959132 J mol
-1
So, our energy balance becomes

T flue
H  3118 J mol-1  959132 J mol-1  C pflue dT  800000 J mol-1
298.15 K

T flue
So, C pflue dT = 162250 J mol-1. So, we can put the flue gas composition into the heat capacity
298.15 K
integral and try different final temperatures until we get this value:
Updated 18/01/2017 41
ICPH*R
T1 (K) T2 (K) A B (1/K) C (1/K ) 2
D (K ) 2
ICPH (K) (J/mol)
298.15 543.5519 73.77225 0.015066 0 -96210 1.95E+04 162250.00
T2
1
    
Cp B 2 C 3 1
dT A T2 T1 
ICPH  T2 T12 T2 T13 D 
R 2 3 T2 T1
T1
CH4 1.702 9.08E-03 -2.16E-06 0

C2H6 1.131 1.92E-02 -5.56E-06 0
O2 3.369 5.06E-04 0 -2.27E+04
N2 3.28 5.93E-04 0 4.00E+03
CO2 5.457 1.05E-03 0 -1.16E+05
H2O 3.47 1.45E-03 0 1.21E+04
A flue gas temperature of 543.6 K = 270C satisfies the energy balance.

On a basis of 1 mol of gas entering, we have 0.15 mol SO2, 0.2 mol O2, and 0.65 mol N2 in the inlet stream.
If 86% of the SO2 is further oxidized to SO3, then 0.86*0.15 = 0.129 mol SO2 is oxidized, producing 0.129
mol SO3 by the reaction SO2 + ½ O2  SO3. This also consumes ½ * 0.129 = 0.0645 mol O2. So, in the
exit stream we have 0.021 mol SO2, 0.129 mol SO3, 0.1355 mol O2, and 0.65 mol N2. Notice that for every
1 mol of gas entering, we only have a total of 0.9355 mol leaving.
Since the entrance and exit temperatures are different, to compute the net heat removal requirement we
could either compute the heat required to heat the reactants from 400C to 500C and then compute the
heat of reaction at 500C, or we could compute the heat of reaction at 400 C and then compute the heat
required to heat the products from 400C to 500C. The net heat requirement (the sum of these 2 steps)
will be the same either way. Of course, we could also cool the whole inlet stream to 298K, add the heat of
reaction at that temperature, and then heat the whole product stream to 500°C. That would also give the
same answer.
Updated 18/01/2017 42
Using the handy spreadsheet from the notes, we can compute the heat of reaction at 400C as follows:
1 1 1 
Temperature of Interest Reaction at T 0 Integral Reaction at T
1
RT 
C p dT    A  T  T0  
T  2

B 2

T  T02 
3

C 3

T  T03   D    
 T T0  
298.15 673.15 -98.890 0.053 -98.596

  1 1 
o
,T   H rxn ,T0  R   A  T  T0  
o B 2
 
T  T02 
C 3
 
T  T03   D   
Standard Heat  2 3  T T0  
Name coefficient at T 0 (kJ/mol) A B (1/K) C (1/K2) D (K2) niHf,i niAi niBi niCi niDi
SO2 -1 -296.83 5.699 8.01E-04 0.00E+00 -1.02E+05 2.97E+02 -5.70E+00 -8.01E-04 0.00E+00 1.02E+05
O2 -0.5 0 3.639 5.06E-04 0.00E+00 -2.27E+04 0.00E+00 -1.82E+00 -2.53E-04 0.00E+00 1.14E+04
SO3 1 -395.72 8.06 1.06E-03 0.00E+00 -2.03E+05 -3.96E+02 8.06E+00 1.06E-03 0.00E+00 -2.03E+05
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
A B (1/K) C (1/K2) D (K2)

0.5415 2.00E-06 0.00E+00 -9.00E+04
So, the heat of reaction at 400C is -98.596 kJ per mol of SO2 reacted. If 0.129 mol reacts, then the heat
released is -98.596*0.129 = -12.719 kJ.
Now, we want to find the heat input required to increase the temperature of the products from 400C to
500C. We can make a modified heat capacity integral spreadsheet that adds up the total heat capacity of
the mixture components to get the total heat capacity and then computes the integral. This is shown below,
and can be downloaded by clicking here.
Total Values for Mixture T2

 1 1
C (1/K2) D (K2) ICPH (K*mol)
    
Cp B C 3
dT  A T2  T1   T22  T12 
T1 (K) T2 (K) A B (1/K)
ICPH  T2  T13  D   
673.15 773.15 3.78E+00 6.07E-04 0.00E+00 -2.88E+04 416.822 R 2 3  T2 T1 
T1
Species Values Values * Moles
2 2 2 2
Species Moles A B (1/K) C (1/K ) D (K ) A mol B (mol/K) C (mol/K ) D (mol K )
SO2 0.021 5.699 0.000801 0.00E+00 -1.02E+05 1.20E-01 1.68E-05 0.00E+00 -2.13E+03
O2 0.1355 3.639 0.000506 0.00E+00 -2.27E+04 4.93E-01 6.86E-05 0.00E+00 -3.08E+03
SO3 0.129 8.06 0.001056 0.00E+00 -2.03E+05 1.04E+00 1.36E-04 0.00E+00 -2.62E+04
N2 0.65 3.28 5.93E-04 0.00E+00 4.00E+03 2.13E+00 3.85E-04 0.00E+00 2.60E+03
0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00
So, the heat capacity integral is 416.8 K mol. Notice that since we multiplied the polynomial coefficients
by the number of moles of each species, the integral is now in terms of the total heat capacity for the number
of moles specified and has units of K mol, rather than just K. Multiplying by R = 0.008314 kJ mol K
-1
gives the heat requirement as 3.465 kJ. So, the reaction releases 12.719 kJ, and 3.465 kJ of this is required
to heat the products to 500C. Therefore, -12.719 + 3.465 = -9.25 kJ has to be removed per mole of feed
gas fed to the catalytic converter.
Updated 18/01/2017 43

This problem is very much like the previous one. We will work it on the basis of 1 mol of CO fed to the
reactor. Thus, the feed is 1 mol CO and 1 mol H2O. If 65% of the H2O (and by stoichiometry therefore alse
65% of the CO) is converted, then the product is 0.35 mol CO, 0.35 mol H2O, 0.65 mol CO2, and 0.65 mol
H2
reactants from 125C to the final temperature of 425C (698.15 K), and then compute the heat of reaction
at 425C. We can use a spreadsheet just like the one used in the last problem:
Total Values for Mixture T2
1 1
 R dT  AT  T   2 T  C3 T 
T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPH (K*mol) Cp B
ICPH  2 1 2
2
 T12  2
3
 T13  D   
398.15 698.15 6.85E+00 2.01E-03 0.00E+00 9.00E+03 2393.554  T2 T1 
T1
Species Values Values * Moles
2 2 2 2
Species Moles A B (1/K) C (1/K ) D (K ) A mol B (mol/K) C (mol/K ) D (mol K )
CO 1 3.376 5.57E-04 0.00E+00 -3.10E+03 3.38E+00 5.57E-04 0.00E+00 -3.10E+03
H2O 1 3.47 1.45E-03 0.00E+00 1.21E+04 3.47E+00 1.45E-03 0.00E+00 1.21E+04
0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00
Multiplying the heat capacity integral by R gives Q = 2393.5*0.008314 = 19.90 kJ required to heat the feed
from 398.15 K to 698.15 K.
Now, we compute the heat of reaction at 698.15 K in the same way as in the lecture notes and the previous
problem:
Updated 18/01/2017 44

1 1 1 
Temperature of Interest Reaction at T 0 Integral Reaction at T
1
RT 
C p dT    A  T  T0  
T  2

B 2

T  T02 
3

C 3

T  T03   D    
 T T0  
298.15 698.15 -41.166 0.591 -37.734

  1 1 
o
,T   H rxn ,T0  R   A  T  T0  
o

B 2
2
 
T  T02 
C 3
3
 
T  T03   D   
 T T0  
Standard Heat 
2 2
Name coefficient at T 0 (kJ/mol) A B (1/K) C (1/K ) D (K ) niHf,i niAi niBi niCi niDi
CO -1 -110.525 3.376 5.57E-04 0.00E+00 -3.10E+03 1.11E+02 -3.38E+00 -5.57E-04 0.00E+00 3.10E+03
H2O -1 -241.818 3.47 1.45E-03 0.00E+00 1.21E+04 2.42E+02 -3.47E+00 -1.45E-03 0.00E+00 -1.21E+04
CO2 1 -393.509 5.457 1.05E-03 0.00E+00 -1.16E+05 -3.94E+02 5.46E+00 1.05E-03 0.00E+00 -1.16E+05
H2 1 0 3.249 4.22E-04 0.00E+00 8.30E+03 0.00E+00 3.25E+00 4.22E-04 0.00E+00 8.30E+03
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
0.00E+00 0.00E+00 0.00E+00 0.00E+00 0.00E+00
A B (1/K) C (1/K ) D (K )
2 2
1.86 -5.40E-04 0.00E+00 -1.16E+05

So, the heat of reaction is ---37.734 kJ per mol of CO reacted. If 0.6 mol of CO reacts, then 37.734*0.6 =
22.64 kJ is released by the reaction. So, the net heat removal rate is 22.64 --- 19.90 = 2.74 kJ per mol of CO
fed to the reactor (1.37 kJ per mole of feed). The exothermicity of the reaction is greater than the heat
needed for the temperature increase, so the net result is that heat has to be removed.

th
BASIS: 100 lbmol DRY flue gases containing 3.00 lbmol CO2 and 11.80 lbmol CO x lbmol O2 and
100-(14.8-x)= 85.2-x lbmol N2. The oil therefore contains 14.80 lbmol carbon; a carbon
balance gives the mass of oil burned:
The oil also contains H2O:
Also H2O is formed by combustion of H2 in the oil in the amount:
Find amount of air entering by N2 & O2 balances. N2 entering in oil:
lbmol N2 entering in the air=(85.2-x)-0.149 =85.051-x
lbmol O2 in flue gas entering with dry air = 3.00 + 11.8/2 + x + 12.448/2 = 15.124 + x lbmol
(CO2) (CO) (O2) (H2O from combustion)
Updated 18/01/2017 45
Total dry air = N2 in air + O2 in air = 85.051 - x + 15.124 + x = 100.175 lbmol
Since air is 21 mol % O2,
O2 in air = 15.124 + x = 21.037 lbmol

N2 in air = 85.051 - x = 79.138 lbmol
N2 in flue gas = 79.138 + 0.149 = 79.287 lbmol
[CHECK: Total dry flue gas = 3.00 + 11.80 + 5.913 + 79.287 = 100.00 lbmol]
Humidity of entering air, sat. at 77 F in lbmol H2O/lbmol dry air, P(sat)=0.4594(psia)
lbmol H2O entering in air:
0.03227⋅100.175⋅lbmol = 3.233 lbmol

If y = lbmol H2O evaporated in the drier, then lbmol H2O in flue gas:
0.116+12.448+3.233+y = 15.797 + y
Entering the process are oil, moist air, and the wet material to be dried, all at
77 F. The "products" at 400 F consist of:
3.00 lbmol CO2
11.80 lbmol CO
5.913 lbmol O2
79.287 lbmol N2
(15.797 + y) lbmol H2O(g)
Energy balance: Q = ΔH = ΔH298 + ΔHP

where Q = 30% of net heating value of the oil:
Reaction upon which net heating value is based:
OIL + (21.024)O2 = (14.8)CO2 + (12.448 + 0.116)H2O(g) + (0.149)N2
− ⋅ ⋅ − ×
To get the "reaction" in the drier, we add to this the following:
Updated 18/01/2017 46
(11.8)CO2 = (11.8)CO + (5.9)O2
⋅ − ⋅ ⋅
(y)H2O(l) = (y)H2O(g)
⋅ ⋅ ⋅
[The factor 0.42993 converts from joules on the basis of moles to BTU on the
basis of lbmol.]
Addition of these three reactions gives the "reaction" in the drier, except for
some O2, N2, and H2O that pass through unchanged. Addition of the
corresponding delta H values gives the standard heat of reaction at 298 K:
For the product stream we need MCPH:
Given
Solve for y = 49.782 lbmol
49.782*18.015/209.13 = 4.288 lb H2O evap. per lb oil burned

If we work from a basis of 1 mole of N2 and 1 mole of C2H2 entering the reactor, then we have 2 moles of
gas entering the reactor, and (since there is no mole change in the reaction) 2 moles of gas leaving the
reactor. If this case is 24.2 mol-% HCN, then the total number of moles of HCN is 2*0.242 = 0.484. The
number of moles of reaction that has occurred (as written) is 0.242 moles, and the number of moles of N2
and C2H2 remaining are (1-0.242) = 0.758 moles each. The total heat supplied to the reactor, on this
basis, will therefore be 0.242 times the heat of reaction at 298 K (conveniently also the temperature at
Updated 18/01/2017 47
which the reactants enter the reactor) plus the heat required to heat 0.748 mol N2, 0.748 mol C2H2 and
0.484 mol HCN from 298 K to 873 K. The heat of reaction is
Hrxn = 2*Hf(HCN(g)) - Hf(N2(g)) - Hf(C2H2(g))
Hrxn = 2*135100 --- 0 --- 227480 = 42720 J mol-1
Since 0.242 mol of reaction occurs, 0.242*42720 = 10338 J of heat input is required to carry out the reaction
at 298.15 K
We can use a handy-dandy spreadsheet like the one provided in the notes to compute the heat capacity
integral for the products:
T2
1 1 
R    
Cp B 2 C 3
ICPH T0,T;A,B,C,D   dT  A T  T0   T  T02  T  T03  D   
T1
2 3  T T0 

ig
T0(K) T (K) A B (1/K)
298.15 873.15 9.42652 0.002587 0 -130522.2 6003.1 49912.6
C2H2 0.758 6.132 1.95E-03 0 -1.30E+05

N2 0.758 3.28 5.93E-04 0 4.00E+03
HCN 0.484 4.736 1.36E-03 0 -7.25E+04
So, the total heat input is 10338 + 49913 = 60250 J per mole of N2 and C2H2 entering the reactor. This is
60250/2 = 30125 J per mole of total inlet or outlet stream, or 60250/0.484 = 124500 J per mole of HCN
produced.
4.42 (7th edition Prob. 4.38) Chlorine is produced by the reaction:

( g ) + 2 C 1 2 ( g ) . The feed stream to the reactor consists of 60 mol-% HCl, 36 mol-% O2, and 4 mol-%
N2, and it enters the reactor at 550°C. If the conversion of HCl is 75% and if the process is isothermal,
how much heat must be transferred to or from the reactor per mole of the entering gas mixture?
BASIS: 1 mole gas entering reactor, containing 0.6 mol HCl, 0.36 mol O2,
and 0.04 mol N2.
HCl reacted = (0.6)(0.75) = 0.45 mol
4HCl(g) + O2(g) = 2H2O(g) + 2Cl2(g)
Evaluate ΔH823 by Eq. (4.23) with
Updated 18/01/2017 48
Heat transferred per mol of entering gas mixture:

th
CO2 + C = 2CO
2C + O2 = 2CO
Eq. (4.22) applies to each reaction:
For (a)
J
H1148  H 298  MCPH * R * T  T0   1.696*105
mol
For (b)
J
H1148  H 298  MCPH * R * T  T0   2.249*105
mol
The combined heats of reaction must be 0
Updated 18/01/2017 49
r H1148b / H1148a  1.327
For 100 mol flue gas and x mol air, moles are:
Flue gas Air Feed mix

CO2 12.8 0 12.8
CO 3.7 0 3.7
O2 5.4 0.21x 5.4 + 0.21x
N2 78.1 0.79x 78.1 + 0.79x
Whence in the feed mix:

Flue gas to air ratio = 100/20.218 = 4.946
Product composition
nCO := 3.7 + 2⋅(12.8 + 5.4 + 0.21⋅19.155 ) = 48.145
nN2= 78.1 + 0.79* 19.155 = 93.232
mol % CO = 34.07 %
mol % N2 = 65.92 %

CH4 + 2O2 = CO2 + 2H2O(g)
CH4 + (3/2)O2 = CO + 2H2O(g)
BASIS: 1 mole of fuel gas consisting of 0.94 mol CH4 and 0.06 mol N2
Air entering contains
1.35 2 0.94 = 2.538 mol O2
2.538 79/21= 9.548 mol N2
Moles CO2 formed by reaction = 0.94⋅0.7 = 0.658

Moles CO formed by reaction = 0.94⋅0.3 = 0.282
Updated 18/01/2017 50
⋅ ⋅
Moles H2O formed by reaction = 0.94⋅2.0 = 1.88
Moles O2 consumed by reaction = 2⋅0.658 + (3/2)⋅0.282 = 1.739
Product gases contain the following numbers of moles:

(1) CO2: 0.658
(2) CO: 0.282
(3) H2O: 1.880
(4) O2: 2.538 - 1.739 = 0.799
(5) N2: 9.548 + 0.060 = 9.608
H P : R  MCPH  298.15K , 483.15K , A, B, C, D    483.15K  298.15K   0.7541*105 J/mol

KJ
Energy balance: H rx  H 298 H P  599.2
mol
⋅ ⋅
From Table C.1: −

=16.635 mol/s
Volumetric flow rate of fuel, assuming ideal gas:

th
C4H8(g) = C4H6(g) + H2(g)

Using the basis of 1 mole C4H8 entering and only 33% reacts. The unreacted C4H8 and the diluent
H2O pass throught the reactor unchanged, and need not be included in the energy balance.
MCPH A B C D T0 tau T
3.2638 4.016 -0.004 0.000000991 8300 298.15 2.677008217 798.15
Then
Updated 18/01/2017 51

Assume Ideal Gas and P = 1 atm
(a)
⋅ − ⋅
(b)
⋅ − ⋅

Assume Ideal Gas and P = 1 atm
(a)
⋅ − ⋅ = -91.8 R
(b)
Updated 18/01/2017 52
⋅ − ⋅

First calculate the standard heat of combustion of propane
C3H8 + 5O2 = 3CO2(g) + 4H2O (g)

Cost = 2.20 Dollars/gal
Estimate the density of propane using the Rackett equation

th
The heat required to take an ideal gas from one temperature to another is given by
T2 T2
  
H  C p dT  R A  BT  CT 2  DT 2 dT
T1 T1

  1 1 
B

H  R  A T2  T1   T22  T12 
 2

C 3
3
 
T2  T13  D    
 T2 T1  
where the temperature dependence of the heat capacity has been expressed in the polynomial form used in
SVNA.
lecture notes, we can use it to evaluate the heat capacity integral in each case.
(a) Using the coefficients for acetylene in the heat capacity polynomial, we have:
Updated 18/01/2017 53
T 1 (K) T 2 (K) A B (1/K) C (1/K2) D (K2) ICPH (K) H (kJ/mol)

298.15 773.15 6.132 1.95E-03 0 -1.30E+05 3.14E+03 26.12
T2
 1 1
R    
Cp B 2 C 3
ICPH  dT  A  T2  T1   T2  T12  T2  T13  D   
2 3  T2 T1 
T1
26.12 kJ/mol is required to heat acetylene from 25C to 500 C.

(b) Using the coefficients for ammonia in the heat capacity polynomial, we have:
298.15 773.15 3.578 3.02E-03 0 -1.86E+04 2.43E+03 20.20
T2
 1 1
 R dT  AT  T   2 T   
Cp B C 3
ICPH  2 1 2
2
 T12  T2  T13  D   
3  T2 T1 
T1
20.20 kJ/mol is required to heat ammonia from 25C to 500 C.

(c ) the heat required to take an ideal gas from one temperature to another is given by
T2 T2
  
T1 T1

  1 1 
B

H  R  A T2  T1   T22  T12 
 2
C 3
3
 
T2  T13  D    
 T2 T1  

Where the temperature dependence of the heat capacity has been expressed in the polynomial form. If we
have set up a spreadsheet to evaluate the heat capacity integral, we can use it to evaluate the heat capacity
integral in each cases.
Using the coefficients for n-butane in the heat capacity polynomial, we have
T0 = 298.15 K and T = 773.15 K
H
71.96 kJ/mol is required to heat n-butane from 250 C to 5000 C.
(d) c ) the heat required to take an ideal gas from one temperature to another is given by
T2 T2
  
T1 T1

  1 1 
B

H  R  A T2  T1   T22  T12 
 2
C 3
3
 
T2  T13  D    
 T2 T1  

Updated 18/01/2017 54
Where the temperature dependence of the heat capacity has been expressed in the polynomial form. If we
have set up a spreadsheet to evaluate the heat capacity integral, we can use it to evaluate the heat capacity
integral in each cases.
Using the coefficients for n-butane in the heat capacity polynomial, we have
T0 = 298.15 K and T = 773.15 K
H
71.96 kJ/mol is required to heat n-butane from 25 C to 500 C.
0 0
(e) Using the coefficients for carbon monoxide in the heat capacity polynomial, we have:
T2
1 1 
R    
Cp B 2 C
ICPH T0,T;A,B,C,D   dT  A T  T0   T  T02  T 3  T03  D   
T1
2 3  T T0 
ICPH (K) H (J/mol)

2 2
T 0(K) T (K) A B (1/K) C (1/K ) D (K )
298.15 773.15 3.376 5.57E-04 0.00E+00 -3.10E+03 1738.9 14457.5
14.5 kJ/mol is required to heat carbon monoxide from 25C to 500 C.
(f) Using the coefficients for ethane in the heat capacity polynomial, we have:
T2
1 1 
R    
Cp B 2 C
T1
2 3  T T0 

2 2
T 0(K) T (K) A B (1/K) C (1/K ) D (K )
298.15 773.15 1.131 1.92E-02 -2.16E-06 0.00E+00 5114.5 42521.6
42.5 kJ/mol is required to heat ethane from 25C to 500 C.

This is just like the previous problem, except that instead of being given the final temperature and
computing Q, we are given Q and must compute the final temperature. To do so, we can just try different
values of the final temperature in the spreadsheet for evaluating the heat capacity integral until we get the
desired Q el to automate this trial and error.
(a) For acetylene starting at 25C, the final temperature for a heat input of 30 kJ/mol is 835 K or 562C:
Updated 18/01/2017 55

298.15 835.36 6.132 1.95E-03 0 -1.30E+05 3.61E+03 30.00
T2
 1 1
R    
Cp B 2 C 3
ICPH  dT  A  T2  T1   T2  T12  T2  T13  D   
2 3  T2 T1 
T1
(b) For ammonia starting at 25C, the final temperature for a heat input of 30 kJ/mol is 964 K or 691C:
298.15 964.00 3.578 3.02E-03 0 -1.86E+04 3.61E+03 30.00
T2
 1 1
R    
Cp B 2 C 3
ICPH  dT  A  T2  T1   T2  T12  T2  T13  D   
2 3  T2 T1 
T1
(c) For n-butane starting at 25C, the final temperature for a heat input of 30 kJ/mol is 534 K or 261 C:
T 1 (K) T 2 (K) A B (1/K) C (1/K2) D (K2) ICPH (K) Q (J/mol)

298.15 534.4073 1.935 3.69E-02 -1.14E-05 0.00E+00 3608 30000
T2
1
    
Cp B 2 C 3 1
dT A T2 T1 
ICPH  T2 T12 T2 T13 D 
R 2 3 T2 T1
T1
(d) For CO2 starting at 25C, the final temperature for a heat input of 30 kJ/mol is 933 K or 660 C:
T 1 (K) T 2 (K) A B (1/K) C (1/K2) D (K2) ICPH (K) Q (J/mol)

298.15 932.9464 5.457 1.05E-03 0.00E+00 -1.16E+05 3608 30000
T2
1
    
Cp B 2 C 3 1
dT A T2 T1 
ICPH  T2 T12 T2 T13 D 
R 2 3 T2 T1
T1
(e) For carbon monoxide starting at 25C, the final temperature for a heat input of 30 kJ/mol is 1248 K or
975C:
Updated 18/01/2017 56
T2
1 1 
R    
Cp B 2 C
T1
2 3  T T0 

2 2
T 0(K) T (K) A B (1/K) C (1/K ) D (K )
298.15 1248.143 3.376 5.57E-04 0.00E+00 -3.10E+03 3608.4 30000.0
(f) For ethane starting at 25C, the final temperature for a heat input of 30 kJ/mol is 664 K or 391C:
T2
1 1 
R    
Cp B 2 C
T1
2 3  T T0 

2 2
T 0(K) T (K) A B (1/K) C (1/K ) D (K )
298.15 664.2338 1.131 1.92E-02 -2.16E-06 0.00E+00 3608.4 30000.0
(g) For hydrogen starting at 25C, the final temperature for a heat input of 30 kJ/mol is 1298 K or
1025C:
T2
1 1 
 R dT  AT  T   2 T   
Cp B C 3
2
 T02  T  T03  D   
T1
3  T T0 

ig
T0(K) T (K) A B (1/K)
298.15 1298.38 3.249 4.22E-04 0 8.30E+03 3608.2 30000.0
(h) For hydrogen chloride starting at 25C, the final temperature for a heat input of 30 kJ/mol is 1277 K
or 1004C:
T2
1 1 
R    
Cp B 2 C 3
ICPH T0,T;A,B,C,D   dT  A T  T0   T  T02  T  T03  D   
T1
2 3  T T0 

ig
T0(K) T (K) A B (1/K)
298.15 1276.95 3.156 6.23E-04 0 1.51E+04 3608.2 30000.0

Given
(a) Guess mole fraction of methane: y=0.5

Given
y = 0.637
Updated 18/01/2017 57
(b)
Guess mole fraction of benzene: y=0.5

Given
y = 0.245
(c)
Guess mole fraction of benzene: y=0.5

Given
y = 0.512
To solve the problem, apply an energy balance equation
TH 1
mc × H = nH  C dT
TH 2
P
mc × H = nH × R × ICPHair
(a) TH 1  1273.15 K and TH 2  308.15 K
Tin = 25°C = 298.15 K, Tboiling = 100°C = 373.15 K, and Tout = 100°C = 373.15 K
ΔH = ΔHliquid + ΔHboiling + ΔHvapor
Updated 18/01/2017 58
H liquid = R × ICPH = 8.314 J·mol1·K 1 × 683.3399 K = 5681.288 J·mol1
H vapor = R × ICPH = 8.314 J·mol1·K 1 × 0 K = 0 J·mol1
H boiling = H latent × mH = 2257 J·g 1 × 18 g·mol1 = 40626 J·mol1
H = 46307.29 J·mol1
For air,
Assume as a basis = 1 mol/s.
ICPHair = 3672.35 K
nH × R × ICPH air
mc = = 0.6593 mol·s 1
H
·
mc
·
= 0.6593
nH
(b)
To solve the problem, apply an energy balance equation
TH 1
mc × H = nH  C dT
TH 2
P
mc × H = nH × R × ICPHair
(a) TH 1  773.15 K and TH 2  308.15 K
Tin = 25°C = 298.15 K, Tboiling = 100°C = 373.15 K, and Tout = 100°C = 373.15 K
Updated 18/01/2017 59
ΔH = ΔHliquid + ΔHboiling + ΔHvapor
H liquid = R × ICPH = 8.314 J·mol1·K 1 × 683.3399 K = 5681.288 J·mol1
H vapor = R × ICPH = 8.314 J·mol1·K 1 × 0 K = 0 J·mol1
H boiling = H latent × mH = 2257 J·g 1 × 18 g·mol1 = 40626 J·mol1
H = 46307.29 J·mol1
For air,
Assume as a basis = 1 mol/s.
ICPHair = 1701.51 K
nH × R × ICPH air
mc = = 0.30548 mol·s 1
H
·
mc
·
= 0.30548
nH

Saturated because the large ΔHlv overwhelms the sensible heat associated with superheat.
Water because it is cheap, available, non-toxic, and has a large ΔHlv.
The lower energy content is a result of the decrease in ΔHlv with increasing T, and hence P.
However, higher pressures allow higher temperature levels.
Updated 18/01/2017 60
(a) The reaction for oxidation of glucose to CO2 and water is the same as the combustion reaction:
C6H12O6(s) + 6 O2(g)  6 CO2(g) + 6 H2O(l)
The heat of reaction for this reaction is
Hrxn = 6*Hf(CO2(g)) + 6*Hf(H2O(l)) --- Hf(C6H12O6(s)) --- 6*Hf(O2(g))
Hrxn = 6*(-393.509) + 6*(-285.83) --- (-1274.4) --- 6*(0) = -2801.6 kJ/mol
(b) The total energy consumption for a 57 kg person (not a very big person) is 150 kJ/kg * 57 kg = 8550
kJ. Given that oxidation of glucose releases 2801.6 kJ/mol, this requires 8550/2802 = 3.05 moles of glucose
per day. The molecular weight of glucose is 180.16 g/mol, so this is 550 g of glucose.
(c) Oxidation of 3.05 moles of glucose produces 18.3 moles of CO2, or 806 g of CO2. Multiplying this by
275 million people gives 2.2210 g/day = 2.2210 kg/day = 222000 metric tons per day = 81 million
11 8
metric tons per year.

th
Assume as a basis, 1 mole of fuel.

0.85 (CH4(g) + 2 O2(g) = CO2(g) + 2 H2O(g))
0.10(C2H6 (g) + 3.5 O2(g) = 2 CO2(g) + 3 H2O(g))
------------------------------------------------------------------
0.85 CH4(g) + 0.10 C2H6(g) + 2.05 O2(g) = 1.05 CO2(g) + 2 H2O(g)
(a)
(b) For complete combustion of 1 mole of fuel and 50% excess air, the exit gas will contain
the following numbers of moles:
Air and fuel enter at 25 C and combustion products leave at 600 C.
⋅ ⋅ ⋅ ⋅
Updated 18/01/2017 61
⋅ ⋅ ⋅ ⋅
⋅ ⋅ ⋅ ⋅
⋅ ⋅ ⋅ ⋅
Updated 18/01/2017 62

Svnas 8e Ism Chapter 04

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SVNAS 8th Edition Annotated Solutions Chapter 4

4.1.(7th edition prob. 4.1)

473.15 1373.15 5.699 8.01E-04 0 -1.02E+05 5.65E+03

4.2 (7th edition Prob. 4.2)

T1 (K) T2 (K) A B (1/K) C (1/K2) D (K2) ICPH (K)

This can easily be done in a spreadsheet.

g Propylene 1.637 22.706 -6.915 0 9.15 76.05 530.95

4.4 (7th edition Prob. 4.3)

n = 0.59 lbmol s-1

capacity integral from 323 to 1153 K, we get H/R = 11350 K

4.6. (7 edition prob. 4.5)

Define δ as the difference between the two heat capacities:

This readily reduces to:

4.7. (7th edition prob. 4.6)

For consistency with the problem statement, we rewrite Eq. (4.8) as

As in the preceding problem,

Define δ as the difference between the two heat capacities:

This readily reduces to:

Making the substitution τ = T2/ T1 yields the required answer.

4.8. (7th edition prob. 4.7)

4.9 (7th edition prob. 4.8)

4.10 (7th edition Prob. 4.9)

H 2  H1    366.3    357.1 J g -1

 0.930  Trn   0.930  0.6583 

H  (273.15  (16))K *0.124767m3.kg 1 *0.0655*102 kPa.K1  210.4kPa.m3 .kg1  210.4kJ.kg1

H  (273.15  (0))K *0.068587m3.kg 1 *0.106*102 kPa.K 1  198.59kPa.m3 .kg1  198.59kJ.kg1

H  (273.15  (12))K *0.045535m3.kg 1 *0.1465*102 kPa.K 1  190.22kPa.m3 .kg1  190.22kJ.kg1

H  (273.15  (26)K *0.029167m3.kg 1 *0.20275*102 kPa.K 1  176.91kPa.m3 .kg1  176.91kJ.kg1

H  (273.15  (40)K *0.019094m3.kg 1 *0.2729*102 kPa.K 1  163.17kPa.m3 .kg1  163.17kJ.kg1

4.12 (7th edition Prob. 4.11)

Likewise, for methanol:

Finally, for carbon tetrachloride,

4.13 (7th edition Prob. 4.12)

dP sat 2772.78  101.325

So, our final answer is H = 31.15 kJ/mol.

7th edition Prob. 4.12, choose ethylbenzene

7th edition Prob. 4.12: Do this for toluene and phenol.

4.14 (7th edition Prob. 4.13)

Differentiate the above equation and determine dP/dT

Using the Clapeyron equation, solve for V

Then using Eq. 3.37, Solve for B

4.15 (7th edition Prob. 4.14)

C (1/K2) D (K2) ICPH (K) H (J/mol)

Finally, for the third step, we have:

C (1/K2) D (K2) ICPH (K) H (J/mol)

And solving it for Tfinal.

4.17 (7th edition Prob. 4.15)

Assume the throttling process is adiabatic and isenthalpic.

4.18 (7th edition Prob. 4.16)

Species Tc Pc Tn Trn Tr25C n 25C f

4.19 (7 edition Prob. 4.17)

1st law: dQ = dU dW = CV dT + P dV (A)

Ideal gas: P V = R T and P dV + V dP = R dT

Since P V = const then P V 1

Combines with (B) to yield:

Combines with (A) to give:

Which reduces to:

Since CP is linear in T, the mean heat capacity is the value of

With , and integrating (C):

4.20 (7th edition Prob. 4.18)

integrating spreadsheet gives 2533 K.

4.21 (7th edition Prob. 4.19)

C2H4 + 3O2 = 2CO2 + 2H2O(g)

ΔH298= [2⋅(−241818) + 2⋅(−393509) − 52510] = 1323164 J/mol

H  (273.15  (16))K 0.124767m3.kg 1 0.0655*102 kPa.K1  210.4kPa.m3 .kg1  210.4kJ.kg1

H  (273.15  (0))K 0.068587m3.kg 1 0.106*102 kPa.K 1  198.59kPa.m3 .kg1  198.59kJ.kg1

H  (273.15  (12))K 0.045535m3.kg 1 0.1465*102 kPa.K 1  190.22kPa.m3 .kg1  190.22kJ.kg1

H  (273.15  (26)K 0.029167m3.kg 1 0.20275*102 kPa.K 1  176.91kPa.m3 .kg1  176.91kJ.kg1

H  (273.15  (40)K 0.019094m3.kg 1 0.2729*102 kPa.K 1  163.17kPa.m3 .kg1  163.17kJ.kg1

This is given by Hrxn = Hf(CO2(g) ) + 2Hf(H2O(l)) - Hf(CH4(g)) = 1( -393.51) + 2(-285.83)-(-

= 4( -393.51) + 6(-285.83)-2*(-83.820) = -3121.38 kJ mol-1.

= 2( -393.51) + 2(-285.83)-(-52.510) = -1306.17 kJ mol-1.

= 3( -393.51) + 4(-285.83)-(-104.680) = -2219.47 kJ mol-1.

= 6( -393.51) + 6(-285.83)-2*(-19.710) = -4036.62 kJ mol-1.

= 4( -393.51) + 5(-285.83)-(-125.790) = -2877.4 kJ mol-1.

This is given by Hrxn = 4Hf(CO2(g) ) + 4Hf(H2O(l)) --- *Hf (C4H8 (g))

= 4( -393.51) + 4(-285.83)-(-0.540) = -2716.82 kJ mol-1.

= 4( -393.51) + 4(-285.83)-(-0.540) = -2716.82 kJ mol-1.

= 2( -393.51) + 2(-285.83)-(-166.190) = -1192.49 kJ mol-1.

= 2( -393.51) + 4(-285.83)-2*(-200.660) = -1529.02 kJ mol .

= 2( -393.51) + 4(-285.83)-(-235.100) = -1695.24 kJ mol-1.

Hrxn = 2(-425.609) + 0 --- 2(0) --- 2*(-241.818)= -367.6 kJ mol-1.

(l) Hrxn = 2Hf(H2O(g)) + 2Hf(SO2(g)) - 2Hf(H2S(g)) --- 3 Hf(O2(g))

(x) Hrxn = 2Hf(HCN(g) ) - Hf(C2H2(g)) = 2(135.1) - (227.48) = 42.72 kJ mol-1.