A reactor operating at steady state burns ethane (C2H6) with theoretical amount of air at

25 °C and 1 atm. Assume that the reaction goes to completion and that the combustion
products exit the reactor at 627 °C and 1 atm. Heat transfer from the reactor takes place at
an average surface temperature Tb. Assume kinetic and potential energy effects are
negligible and that T0 = 25 °C.

(a) Write down energy and entropy balances for the reactor, stating your assumptions
clearly.

Solution

The process flow diagram for the system studied is the following:

Combustion Gas

Ethane

Air

Figure 1. Process flow diagram for the system studied.

The chemical reaction which takes place in the reactor is:

7
𝐶2 𝐻6 (𝑔) + 2𝑂2 (𝑔) → 2𝐶𝑂2 (𝑔) + 3𝐻2 𝑂(𝑔)

If we apply the thermodynamics first law to the above system, we get:

𝑄 − 𝑊 = 𝑚𝑠 ℎ̂𝑠 − 𝑚𝑒 ℎ̂𝑒 + 𝑚2 𝑢̂2 − 𝑚1 𝑢̂1

As we are dealing with a continuous steady state and without accumulation system the
above equation can be simplified as:

𝑄 = 𝑚𝑠 ℎ̂𝑠 − 𝑚𝑒 ℎ̂𝑒

For each mol of methane fed, the above equation turns into:
𝑇
7 79 7
𝑄 = 2ℎ̂𝐶𝑂2 + 3ℎ̂𝐻2 𝑂 − ℎ̂𝐶2 𝐻6 − 2ℎ̂𝑂2 + 21 ∙ 2 ∫ 𝐶𝑝𝑁2 𝑑𝑇
𝑇0
Rearranging the above equation, we get;
𝑇 𝑇
79 7
𝑄= ∆𝐻𝑅° + ∫ 𝜐𝑖 𝐶𝑝𝑖 𝑑𝑇 + ∙ ∫ 𝐶𝑝𝑁2 𝑑𝑇
21 2
𝑇0 𝑇0

If we apply thermodynamics second law, we get:

𝛿𝑄
∆𝑆 = 𝑚𝑠 𝑠̂𝑠 − 𝑚𝑒 𝑠̂𝑒 + 𝑚2 𝑠̂2 − 𝑚1 𝑠̂1 = ∫ + ∆𝑆𝑔
𝑇

In the same way as the case above assuming that we are dealing with a continuous, steady
state and without accumulation system, we get:

∆𝑆 = 𝑚𝑠 𝑠̂𝑠 − 𝑚𝑒 𝑠̂𝑒

For each mol of methane fed, the above equation turns into:
𝑇
𝑑𝑇 79 7 𝑇 𝑑𝑇 𝑃1
∆𝑆 = ∆𝑆𝑅° + ∫ 𝜐𝑖 𝐶𝑝𝑖 + 21 ∙ 2 ∫ 𝐶𝑝𝑁2 − 𝑅 ln ( )
𝑇0 𝑇 𝑇0 𝑇 𝑃0

The standard entropy of reaction can be written as:

∆𝐻𝑅° − ∆𝐺𝑅°
∆𝑆𝑅° =
𝑇0

If we assume that the process takes place at constant pressure P1 = P0, we get:

∆𝐻𝑅° − ∆𝐺𝑅° 𝑇
𝑑𝑇 79 7 𝑇 𝑑𝑇
∆𝑆 = + ∫ 𝜐𝑖 𝐶𝑝𝑖 + 21 ∙ 2 ∫ 𝐶𝑝𝑁2
𝑇0 𝑇0 𝑇 𝑇0 𝑇

The standard heat of reaction and standard free energy are given by:
° ° °
∆𝐻𝑅° = 2∆𝐻𝑓𝐶𝑂2
+ 3∆𝐻𝑓𝐻2𝑂
− ∆𝐻𝑓𝐶2 𝐻6

° ° °
∆𝐺𝑅° = 2∆𝐺𝑓𝐶𝑂2
+ 3∆𝐺𝑓𝐻2𝑂
− ∆𝐺𝑓𝐶2 𝐻6

The standard enthalpies and free energy of formation, extracted from Smith and Van Ness,
are given by:

°
𝐽 °
𝐽 °
𝐽
∆𝐻𝑓𝐶𝑂 = −393,509 ∆𝐻𝑓𝐻2𝑂
= −241,818 ∆𝐻𝑓𝐶2 𝐻6
= −83820
2
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙

°
𝐽 °
𝐽 °
𝐽
∆𝐺𝑓𝐶𝑂 = −394,359 ∆𝐻𝑓𝐻2𝑂
= −228,572 ∆𝐻𝑓𝐶2 𝐻6
= −31,855
2
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
The standards heats of reaction and free energy, are given by:
 𝐽 𝐽 𝐽
∆𝐻𝑅° = 2 (−393,509 ) + 3 (−241,818 ) − (−83820 )
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
𝐽 𝐽 𝐽
∆𝐺𝑅° = 2 (−394,359 ) + 3 (−228,572 ) − (−31,855 )
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
𝐽
∆𝐻𝑅° = −1,428,652
𝑚𝑜𝑙
𝐽
∆𝐺𝑅° = −1,442,579
𝑚𝑜𝑙
The heat capacities of carbon dioxide, water, oxygen, and ethane, are given by:

𝐶𝑝𝐶𝑂2
= 5.457 + 1.045 ∙ 10−3 𝑇 − 1.557 ∙ 105 𝑇 −2
𝑅
𝐶𝑝𝐻2 𝑂
= 3.47 + 1.45 ∙ 10−3 𝑇 + 0.121 ∙ 105 𝑇 −2
𝑅
𝐶𝑝𝑂2
= 3.639 + 0.506 ∙ 10−3 𝑇 − 0.227 ∙ 105 𝑇 −2
𝑅
𝐶𝑝𝐶2 𝐻6
= 1.131 + 19.225 ∙ 10−3 𝑇 − 5.561 ∙ 10−6 𝑇 2
𝑅
The value of 𝜐𝑖 𝐶𝑝𝑖 can be estimated as:

𝜐𝑖 𝐶𝑝𝑖 = ∆𝐴 + ∆𝐵 ∙ 𝑇 + ∆𝐶 ∙ 𝑇 2 + ∆𝐷 ∙ 𝑇 −2

For the present case, we have:

7
∆𝐴 = 2 ∙ 5.457 + 3 ∙ 3.47 − ∙ 3.639 − 1.131 = 7.456
2
7
∆𝐵 = (2 ∙ 1.045 + 3 ∙ 1.45 − ∙ 0.506 − 19.225) ∙ 10−3 = −1.4556 ∙ 10−2
2
7
∆𝐶 = (2 ∙ 0 + 3 ∙ 0 − ∙ 0 − (−5.561)) ∙ 10−6 = 5.561 ∙ 10−6
2

7
∆𝐷 = (2 ∙ (−1.557) + 3 ∙ 0.121 − ∙ (−0.227) − 0) ∙ 105 = −1.9565 ∙ 105
2
In this way, we have:

𝜐𝑖 𝐶𝑝𝑖 = 7.456 − 1.4556 ∙ 10−2 ∙ 𝑇 + 5.561 ∙ 10−6 ∙ 𝑇 2 − 1.9565 ∙ 105 ∙ 𝑇 −2

For the first integral, we have:

 𝑇 900.15
∫ 𝜐𝑖 𝐶𝑝𝑖 𝑑𝑇 = 8.314 ∫ (7.456 − 1.4556 ∙ 10−2 ∙ 𝑇 + 5.561 ∙ 10−6 ∙ 𝑇 2 − 1.9565 ∙ 10−5 ∙ 𝑇 −2 )𝑑𝑇
𝑇0 298.15

𝑇
𝐽
∫ 𝜐𝑖 𝐶𝑝𝑖 𝑑𝑇 = 853.38
𝑇0 𝑚𝑜𝑙

For the second integral, we have:

𝑇 900.15
𝑑𝑇 𝑑𝑇
∫ 𝜐𝑖 𝐶𝑝𝑖 = 8.314 ∫ (7.456 − 1.4556 ∙ 10−2 ∙ 𝑇 + 5.561 ∙ 10−6 ∙ 𝑇 2 − 1.9565 ∙ 10−5 ∙ 𝑇 −2 )
𝑇0 𝑇 298.15 𝑇

𝑇
𝑑𝑇 𝐽
∫ 𝜐𝑖 𝐶𝑝𝑖 = 4.178
𝑇0 𝑇 𝑚𝑜𝑙 ∙ 𝐾

The heat capacity of nitrogen is given by:

𝐶𝑝𝑁2
= 3.28 + 0.593 ∙ 10−3 𝑇 + 0.04 ∙ 105 𝑇 −2
𝑅
The third integral, is given by:
𝑇 𝑇
∫ 𝐶𝑝𝑁2 𝑑𝑇 = 8.314 ∫ 3.28 + 0.593 ∙ 10−3 𝑇 + 0.04 ∙ 105 𝑇 −2 𝑑𝑇
𝑇0 𝑇0

𝑇
𝐽
∫ 𝐶𝑝𝑁2 𝑑𝑇 = 18269.35
𝑇0 𝑚𝑜𝑙

The fourth integral is given by:

𝑇 𝑇
𝑑𝑇 𝑑𝑇
∫ 𝐶𝑝𝑁2 = 8.314 ∫ 3.28 + 0.593 ∙ 10−3 𝑇 + 0.04 ∙ 105 𝑇 −2
𝑇0 𝑇 𝑇0 𝑇

𝑇
𝑑𝑇 𝐽
∫ 𝐶𝑝𝑁2 = 33.27
𝑇0 𝑇 𝑚𝑜𝑙 ∙ 𝐾

The term ∆𝑆𝑅° results in:

𝐽 𝐽
∆𝐻 °
− ∆𝐺 ° −1,428,652 + 1,442,579
∆𝑆𝑅° =
𝑅 𝑅
= 𝑚𝑜𝑙 𝑚𝑜𝑙
𝑇0 298.15

∆𝐻𝑅° − ∆𝐺𝑅° 𝐽
= 46.711
𝑇0 𝑚𝑜𝑙 ∙ 𝐾

Evaluating the heat released, we get:

 𝑇 𝑇
79 7
𝑄 = ∆𝐻𝑅° + ∫ 𝜐𝑖 𝐶𝑝𝑖 𝑑𝑇 + 21 ∙ 2 ∫ 𝐶𝑝𝑁2 𝑑𝑇
𝑇0 𝑇0

𝐽 𝐽 79 7 𝐽
𝑄 = −1,428,652 + 853.38 + 21 ∙ 2 ∙ 18269.35
𝑚𝑜𝑙 𝑚𝑜𝑙 𝑚𝑜𝑙
𝐽
𝑄 = −1,187,252.18
𝑚𝑜𝑙
Evaluating the change of entropy of the system, we get:

∆𝐻𝑅° − ∆𝐺𝑅° 𝑇
𝑑𝑇 79 7 𝑇 𝑑𝑇
∆𝑆 = + ∫ 𝜐𝑖 𝐶𝑝𝑖 + 21 ∙ 2 ∫ 𝐶𝑝𝑁2
𝑇0 𝑇0 𝑇 𝑇0 𝑇

𝐽 𝐽 79 7 𝐽
∆𝑆 = 46.711 + 4.178 + 21 ∙ 2 ∙ 33.27
𝑚𝑜𝑙 ∙ 𝐾 𝑚𝑜𝑙 ∙ 𝐾 𝑚𝑜𝑙 ∙ 𝐾
𝐽
∆𝑆 = 488.94
𝑚𝑜𝑙 ∙ 𝐾

(c) Evaluate the total exergy (in kJ) of each mass entering and leaving the reactor, per kmol
of fuel.

As we are dealing with an open system, the exergy of each stream flowrate neglecting
potential and is given by:

𝜓 = (ℎ − ℎ0 ) − 𝑇0 (𝑆 − 𝑆0 )

Where h0, s0, and T0 corresponds to the exergy of the death state, in this case P0 = 1 atm,
and T0 = 298.15 K.

For the case of ethane and air, its inlet conditions are exactly the same the death state
conditions, in this way, the exergy of ethane and air are given by:

𝑘𝐽
𝜓𝑎𝑖𝑟 = (ℎ0 − ℎ0 ) − 𝑇0 (𝑆0 − 𝑆0 ) = 0
𝑘𝑚𝑜𝑙
𝑘𝐽
𝜓𝑒𝑡ℎ𝑎𝑛𝑒 = (ℎ0 − ℎ0 ) − 𝑇0 (𝑆0 − 𝑆0 ) = 0
𝑘𝑚𝑜𝑙
For the case of the combustion gas, we have that its conditions are different from those of
the death state, then its exergy is given by:
𝑇 𝑇
𝑑𝑇
𝜓𝑔𝑎𝑠 = (ℎ − ℎ0 ) − 𝑇0 (𝑆 − 𝑆0 ) = ∫ 𝜐𝑖 𝐶𝑝𝑖 𝑑𝑇 − 𝑇0 ∫ 𝜐𝑖 𝐶𝑝𝑖
𝑇0 𝑇0 𝑇

The integrals can be calculated as follows:

 𝑇 𝑇
7 79
∫ 𝜐𝑖 𝐶𝑝𝑖 𝑑𝑇 = ∫ (2𝐶𝑝𝐶𝑂2 + 3𝐶𝑝𝐻2 𝑂 + ∙ 𝐶𝑝 ) 𝑑𝑇
𝑇0 𝑇0 2 21 𝑁2

Let be:
7 79
𝐶𝑝𝑎𝑣𝑒 = 2𝐶𝑝𝐶𝑂2 + 3𝐶𝑝𝐻2 𝑂 + ∙ 𝐶𝑝
2 21 𝑁2
We have:
𝑇 𝑇
𝑑𝑇
𝜓𝑔𝑎𝑠 = ∫ 𝐶𝑝𝑎𝑣𝑒 𝑑𝑇 − 𝑇0 ∫ 𝐶𝑝𝑎𝑣𝑒
𝑇0 𝑇0 𝑇

The average heat capacity, can be calculated as:

𝐶𝑝𝑎𝑣𝑒 = ∆𝐴 + ∆𝐵 ∙ 𝑇 + ∆𝐶 ∙ 𝑇 2 + ∆𝐷 ∙ 𝑇 −2

7 79
∆𝐴 = 2 ∙ 5.457 + 3 ∙ 3.47 + ∙ ∙ 3.28 = 64.51
2 21
7 79
∆𝐵 = (2 ∙ 1.045 + 3 ∙ 1.45 + ∙ ∙ 0.593) ∙ 10−3 = 0.01425
2 21

∆𝐶 = 0

7 79
∆𝐷 = (2 ∙ (−1.557) + 3 ∙ 0.121 + ∙ ∙ 0.04) ∙ 105 = −2.2243 ∙ 105
2 21
In this way the average heat capacity results in:

𝐶𝑝𝑎𝑣𝑒 = 64.51 + 0.01425 ∙ 𝑇 − 2.2243 ∙ 105 ∙ 𝑇 −2

The first integral results in:

𝑇 900.15
∫ 𝐶𝑝𝑎𝑣𝑒 𝑑𝑇 = ∫ (64.51 + 0.01425 ∙ 𝑇 − 2.2243 ∙ 105 ∙ 𝑇 −2 )𝑑𝑇
𝑇0 298.15

𝑇
𝐽
∫ 𝐶𝑝𝑎𝑣𝑒 𝑑𝑇 = 43974.83
𝑇0 𝑚𝑜𝑙

The second integral results in:

𝑇 𝑇
𝑑𝑇 𝑑𝑇
∫ 𝐶𝑝𝑎𝑣𝑒 = ∫ (64.51 + 0.01425 ∙ 𝑇 − 2.2243 ∙ 105 ∙ 𝑇 −2 )
𝑇0 𝑇 𝑇0 𝑇

𝑇
𝑑𝑇 𝐽
∫ 𝐶𝑝𝑎𝑣𝑒 = 79.86
𝑇0 𝑇 𝑚𝑜𝑙 ∙ 𝐾
Evaluating the exergy of the combustion gas, results:

𝐽 𝐽
𝜓𝑔𝑎𝑠 = 43974.83 − 298.15 𝐾 ∙ 79.86
𝑚𝑜𝑙 𝑚𝑜𝑙 ∙ 𝐾
𝑘𝐽
𝜓𝑔𝑎𝑠 = 20164.57
𝑘𝑚𝑜𝑙