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1. A new process for the manufacture of acetylene has been proposed.

The process will


involve the dehydrogenation of ethane over a suitable catalyst (yet to be found). Pure
ethane will be fed to a reactor and a mixture of acetylene, hydrogen, and unreacted
ethane will be withdrawn. The reactor will operate at 101.3 Kpa total pressure and at
some as yet unspecified temperature T. The reaction
𝑪𝟐 𝑯𝟔 → 𝑪𝟐 𝑯𝟐 + 𝟐𝑯𝟐
may be assumed to be the only reaction occurring in the proposed reactor. The
following data on the heats of formation of ethane and acetylene are available.

∆𝑮𝒐𝒇 𝟐𝟗𝟖 (kJ/mole) ∆𝑯𝒐𝒇 𝟐𝟗𝟖 (kJ/mole)

Ethane -32.908 -84.724


Acetylene 209.340 226.899

Entropy (J/mole. K)
Ethane 229.65
Acetylene 200.95

The standard states of these materials are taken as the pure components at 298 K and
a pressure of 101.3 Kpa. The following data on the absolute entropies of the
hydrocarbons at 298 K are available.

a. What is the standard Gibbs free energy change at 25oC for the reaction as
written?
∆𝐺𝑓𝑜298 𝐶2 𝐻6 = −32.908 kJ/mole
∆𝐺𝑓𝑜298 𝐶2 𝐻2 = 209.340 kJ/mole
∆𝐺𝑓𝑜298 𝐻2 = 0 kJ/mole
𝐶2 𝐻6 → 𝐶2 𝐻2 + 2𝐻2

The standard Gibbs free energy change at 25oC can be calculated with following
formula:
𝑜
∆𝐺298 = ∆𝐺𝑓𝑜 298 𝐶2 𝐻2 + 2∆𝐺𝑓𝑜298 𝐻2 − ∆𝐺𝑓𝑜298 𝐶2 𝐻6
𝑜
∆𝐺298 = 209.340 kJ⁄mole + 0 kJ⁄mole − (−32.908) kJ⁄mole
𝑜
∆𝐺298 = 242.248 kJ⁄mole
b. What is the standard enthalpy change at 25oC for the reaction as written?
∆𝐻𝑓𝑜 298 𝐶2 𝐻6 = −84.724 kJ/mole
∆𝐻𝑓𝑜 298 𝐶2 𝐻2 = 226.899 kJ/mole
∆𝐻𝑓𝑜 298 𝐻2 = 0 kJ/mole
𝐶2 𝐻6 → 𝐶2 𝐻2 + 2𝐻2

The standard enthalpy energy change at 25oC can be calculated with following formula:
𝑜
∆𝐻298 = ∆𝐻𝑓𝑜 298 𝐶2 𝐻2 + 2∆𝐻𝑓𝑜 298 𝐻2 − ∆𝐻𝑓𝑜 298 𝐶2 𝐻6
𝑜
∆𝐻298 = 226.899 kJ⁄mole + 0 kJ⁄mole − (−84.724) kJ⁄mole
𝑜
∆𝐻298 = 311.623 kJ⁄mole

c. What is the absolute entropy of gaseous hydrogen at 25oC and a pressure of 101.3
Kpa? Use only the above data in evaluating the quantity.
𝑜
∆𝐺298 = 242.248 kJ⁄mole
𝑜
∆𝐻298 = 311.623 kJ⁄mole

In this case, we can apply the equation of the second thermodynamic law :
𝑜 𝑜 𝑜
∆𝐺298 = ∆𝐻298 − 𝑇∆𝑆298
𝑜
242.248 kJ⁄mole = 311.623 kJ⁄mole − 298 × ∆𝑆298
𝑜
∆𝑆298 = 232.685 J/mole K

The standard entropy energy change at 25oC can be calculated with following formula:
𝑜 𝑜 𝑜 𝑜
∆𝑆298 = 𝑆298 𝐶2 𝐻2 + 2𝑆298 𝐻2 − 𝑆298 𝐶2 𝐻6
𝑜
232.685 = 200.95 + 2𝑆298 𝐻2 − 229.65
𝑜
𝑆298 𝐻2 = 130.693 J/mole K
d. What is the equilibrium constant for the reaction at 25oC?
𝑇 = 298 K
𝑅 = 8.314 J⁄K. mole
𝑜
∆𝐺298 = 242.248 kJ⁄mole

The equilibrium constant (K) for this reaction 𝐶2 𝐻6 → 𝐶2 𝐻2 + 2𝐻2 at 25oC can be
calculated with following formula:
∆𝐺 𝑂 −242.248 kJ⁄mole −242248 J⁄mole
ln 𝐾 = − = =
𝑅𝑇 8.314 J⁄mole K × 298 K 8.314 J⁄mole K × 298 K
ln 𝐾 = −97.7764
𝐾 = 3.376 × 10−43

e. If the standard enthalpy change may be assumed to be essentially independent of


temperature, what is the equilibrium constant for the reaction at 827 oC?
𝑇 = 298 K
𝑇 ′ = 827𝑜 C = 1100 K
𝑅 = 8.314 J⁄mole K
𝐾 = 3.376 × 10−43
𝑜
∆𝐻298 = 311.623 kJ⁄mole

The equilibrium constant (K) for this reaction 𝐶2 𝐻6 → 𝐶2 𝐻2 + 2𝐻2 at 827oC can be
calculated with following formula:
𝐾 −∆𝐻𝑜 1 1
ln = ( − ′)
𝐾′ 𝑅 𝑇 𝑇
3.376 × 10−43 − ∆𝐻𝑜 1 1
ln ′
= ( − )
𝐾 𝑅 298𝐾 1100𝐾
3.376 × 10−43 −311623 J⁄mole 1 1
ln ′
= ( − )
𝐾 8.314 J⁄K. mole 298𝐾 1100𝐾
3.376 × 10−43
ln = −91.7033
𝐾′
3.376 × 10−43
= 1.49199 × 10−40
𝐾′
𝐾 ′ = 2.2627 × 10−3
f. If we supply pure ethane at 827oC and a pressure of 101.3 Kpa to the reactor
above and if equilibrium with respect to the reaction
𝑪𝟐 𝑯𝟔 ↔ 𝑪𝟐 𝑯𝟐 + 𝟐𝑯𝟐
Is obtained, what is the composition of the effluent mixture? The reactor may be
assumed to operate isothermally at 101.3 Kpa total pressure. Neglect any other
reactions that may occur.
Assumption:
Ideal Gas
𝑛𝑜 = 1 mol
𝐶2 𝐻6 ↔ 𝐶2 𝐻2 + 2𝐻2
𝑛𝐶2 𝐻6 = 𝑛𝑜 − 𝜀
𝑛𝐶2 𝐻2 = 𝜀 ∑ = 𝑛𝑜 − 𝜀 + 𝜀 + 2𝜀 = 𝑛𝑜 + 2𝜀
𝑛𝐻2 = 2𝜀
K at 827oC, 𝐾 ′ = 2.2627 × 10−3

Then,
𝑛𝑜 −𝜀
𝑦𝐶2 𝐻6 =
𝑛𝑜 +2𝜀
𝜀
𝑦𝐶2 𝐻2 = 𝑛
𝑜 +2𝜀

2𝜀
𝑦𝐻2 = 𝑛
𝑜 +2𝜀

2
(𝑦𝐻2 ) . (𝑦𝐶2 𝐻2 )
𝐾= = 2.2627 × 10−3
(𝑦𝐶2 𝐻6 )
2
2𝜀 𝜀
(𝑛 + 2𝜀 ) . (𝑛 + 2𝜀 )
𝐾= 𝑜 𝑛𝑜 − 𝜀
𝑜
= 2.2627 × 10−3
(𝑛 + 2𝜀 )
𝑜

4𝜀 3
𝐾= = 2.2627 𝑥 × 10−3
(𝑛𝑜 + 2𝜀 )2 (𝑛𝑜 − 𝜀 )
4𝜀 3 = 2.2627 × 10−3 (𝑛𝑜 2 + 4𝜀𝑛𝑜 + 4𝜀 2 )(𝑛𝑜 − 𝜀 )
4𝜀 3 = 2.2627 × 10−3 (𝑛𝑜 3 − 𝜀𝑛𝑜 2 + 4𝜀𝑛𝑜 2 − 4𝜀 2 𝑛𝑜 + 4𝜀 2 𝑛𝑜 − 4𝜀 3 )
4𝜀 3 = 2.2627 × 10−3 (𝑛𝑜 3 + 3𝜀𝑛𝑜 2 − 4𝜀 3 )
4𝜀 3 = 2.2627 × 10−3 𝑛𝑜 3 + 6.7881 × 10−3 𝜀𝑛𝑜 2 − 9.0508 × 10−3 𝜀 3
4.0090508𝜀 3 − 2.2627 × 10−3 𝑛𝑜 3 − 6.7881 × 10−3 𝜀𝑛𝑜 2 = 0

𝑤𝑖𝑡ℎ 𝑡ℎ𝑒 𝑣𝑎𝑙𝑢𝑒 𝑜𝑓 𝑛𝑜 = 1 mol

4.0090508𝜀 3 − 2.2627 × 10−3 − 6.7881 × 10−3 𝜀 = 0

The equation above, yields to :


𝜀 = 0.08946
Then :
1−0.08946
𝑦𝐶2 𝐻6 = 1+2×0.08946 = 0.7718
0.08946
𝑦𝐶2 𝐻2 = 1+2×0.08946 = 0.0761
2×0.08946
𝑦𝐻2 = 1+2×0.08946 = 0.1521
2. Reaksi hidrasi etilen menjadi etanol:
𝑪𝟐 𝑯𝟒 (𝒈) + 𝑯𝟐 𝑶(𝒈) → 𝑪𝟐 𝑯𝟓 𝑶𝑯(𝒈)
Berlangsung pada suhu 200oC dan tekanan 1 atm dengan reaktan pada awal reaksi yang
terdiri dari 1 mol kukus (uap) dan 1 mol etilen. Tentukanlah derajat keberlangsungan
reaksi (ε1) pada saat reaksi mencapai kesetimbangan. Tentukan pula ε2 bila pada
campuran ditambahkan 10 mol gas inert per mol etilen. Apakah efek penambahan
diluent (gas inert) menggeser kesetimbangan reaksi pada arah yang sama dengan
penurunan tekanan sistem?
Based on table C-4 (Chemical Engineering Thermodynamics 6th ed) :
∆𝐺𝑓𝑜298 𝐶2 𝐻4 = 68460 J/mole
∆𝐺𝑓𝑜298 𝐶2 𝐻5 𝑂𝐻 = −168490 J/mole
∆𝐺𝑓𝑜298 𝐻2 𝑂 = −228572 J/mole

𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) → 𝐶2 𝐻5 𝑂𝐻(𝑔)

The standard Gibbs free energy change at 25oC can be calculated with following formula:
𝑜
∆𝐺298 = ∆𝐺𝑓𝑜298 𝐶2 𝐻5 𝑂𝐻 − ∆𝐺𝑓𝑜298 𝐻2 𝑂 − ∆𝐺𝑓𝑜298 𝐶2 𝐻4
𝑜
∆𝐺298 = −168490 J⁄mole − (−228572) J⁄mole − 68460 J⁄mole
𝑜
∆𝐺298 = −8378 J⁄mole

Based on table C-4 (Chemical Engineering Thermodynamics 6th ed) :


∆𝐻𝑓𝑜 298 𝐶2 𝐻4 = 52510 kJ/mole
∆𝐻𝑓𝑜 298 𝐶2 𝐻5 𝑂𝐻 = −235100 kJ/mole
∆𝐻𝑓𝑜 298 𝐻2 𝑂 = −241818 kJ/mole
𝐶2 𝐻6 → 𝐶2 𝐻2 + 2𝐻2

The standard enthalpy change energy change at 25oC can be calculated with following
formula:
𝑜
∆𝐻298 = ∆𝐻𝑓𝑜 298 𝐶2 𝐻5 𝑂𝐻 − ∆𝐻𝑓𝑜 298 𝐻2 𝑂 − ∆𝐻𝑓𝑜 298 𝐶2 𝐻4
𝑜
∆𝐻298 = −235100 J⁄mole − (−241818) J⁄mole − 52510 J⁄mole
𝑜
∆𝐻298 = −45792 J⁄mole

Equilibrium Constant
𝑇 = 298 K
𝑅 = 8.314 J⁄K. mole
𝑜
∆𝐺298 = 51622 J⁄mole

The equilibrium constant (K) for this reaction 𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) → 𝐶2 𝐻5 𝑂𝐻(𝑔) at 25oC can
be calculated with following formula:
−∆𝐺 𝑂 −8378 J⁄mole
ln 𝐾 = − =−
𝑅𝑇 8.314 J⁄K. mole × 298 K
ln 𝐾 = 3.3815
𝐾 = 29.4159

Equilibrium Constant at 200oC


𝑇0 = 298 K
𝑇 = 200𝑜 C = 473 K
𝑅 = 8.314 J⁄K. mole
𝐾 = 29.4159
𝑜
∆𝐻298 = −45792 J⁄mole
𝑛𝐶2𝐻4 = 𝑛𝐻2𝑂 = 𝑛𝑜 = 1 mole

The equilibrium constant (K) for this reaction 𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) → 𝐶2 𝐻5 𝑂𝐻(𝑔) at 200oC
can be calculated with evaluating the following formulas :
∆𝐺 𝑜 ∆𝐺0𝑜 − ∆𝐻0𝑜 ∆𝐻0𝑜 1 𝑇 ∆𝐶𝑃0 𝑇
∆𝐶𝑃0 𝑑𝑇
= + + ∫ 𝑑𝑇 − ∫
𝑅𝑇 𝑅𝑇0 𝑅𝑇 𝑇 𝑇0 𝑅 𝑇0 𝑅 𝑇
∆𝐺 𝑜
ln 𝐾 = −
𝑅𝑇

Firstly we will determine the value of the first integral on the right side of the first equation.
To calculate that speci, we must firstly check the Table C.1 on Chemical Engineering
Thermodynamics 6th ed. , to get these data :
∆𝐴 = 3.518 − 1.424 − 3.470 = −1.376
∆𝐵 = (20.001 − 14.394 − 1.450) × 10−3 = 4.157 × 10−3
∆𝐶 = (−6.002 + 4.392) × 10−6 = −1.610 × 10−6
∆𝐷 = −1.21 × 104

𝑇
∆𝐶𝑃0 ∆𝐵 2 2 ∆𝐶 3 3 ∆𝐷 𝜏 − 1
∫ 𝑑𝑇 = ∆𝐴𝑇0 (𝜏 − 1) + 𝑇0 (𝜏 − 1) + 𝑇0 (𝜏 − 1) + ( )
𝑇0 𝑅 2 3 𝑇0 𝜏
𝑇 473
Where 𝜏 = 𝑇 = 298 = 1.587, so the calculation of the calculation above yields to :
0

𝑇
∆𝐶𝑃0
∫ 𝑑𝑇 = −17.971
𝑇0 𝑅

Then, we must calculate the second integral spesi of the right side, by using the following
equation :
𝑇
∆𝐶𝑃0 𝑑𝑇 ∆𝐷 𝜏+1
∫ = ∆𝐴 ln 𝜏 + [∆𝐵𝑇0 + (∆𝐶𝑇02 + 2 2 ) ( )] (𝜏 − 1)
𝑇0 𝑅 𝑇 𝜏 𝑇0 2
𝑇 473
Where 𝜏 = 𝑇 = 298 = 1.587, so the calculation of the calculation above yields to :
0

𝑇
∆𝐶𝑃0 𝑑𝑇
∫ = −0.05794
𝑇0 𝑅 𝑇
These calculations yields to :
∆𝐺 𝑜 −8378 + 45792 −45792 −17.971
= + + + 0.05794
𝑅𝑇 8.314 × 298 8.314 × 473 473
∆𝐺 𝑜
= 3.4766
𝑅𝑇

Finally,
ln 𝐾 = −3.4766
𝐾 = 3.0913 × 10−2
Calculation of 𝜺𝟏
𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) → 𝐶2 𝐻5 𝑂𝐻(𝑔)
𝑛𝐶2 𝐻5 𝑂𝐻 = 𝜀
𝑛𝐶2 𝐻4 = 𝑛𝑜 − 𝜀 ∑ = 𝑛𝑜 − 𝜀 + 𝜀 + 𝑛𝑎 − 𝜀 = 𝑛𝑎 + 𝑛𝑜 − 𝜀 = 2 − 𝜀
𝑛𝐻2 𝑂 = 𝑛𝑎 − 𝜀
K at 200oC, 𝐾 ′ = 3.0913 × 10−2
𝑛𝑜 = 𝑛𝑎 = 1 mole

Then,
𝜀
𝑦𝐶2 𝐻5 𝑂𝐻 = 2−𝜀
1−𝜀
𝑦𝐶2 𝐻4 = 2−𝜀
1−𝜀
𝑦𝐻2 𝑂 = 2−𝜀

(𝑦𝐶2 𝐻5 𝑂𝐻 )
𝐾= = 3.0913 × 10−2
(𝑦𝐶2 𝐻4 ). (𝑦𝐻2 𝑂 )
𝜀
(2 − 𝜀 )
𝐾= = 3.0913 × 10−2
1−𝜀 1−𝜀
(2 − 𝜀 ) (2 − 𝜀 )

𝜀 (2 − 𝜀 )
= 3.0913 × 10−2
(1 − 𝜀 ). (1 − 𝜀 )
2𝜀 − 𝜀 2 = 3.0913 × 10−2 (1 − 2𝜀 − 𝜀 2 )
2𝜀 − 𝜀 2 = 3.0913 × 10−2 − 6.1826 × 10−2 𝜀 − 3.0913 × 10−2 𝜀 2
0.9691𝜀 2 − 2.0618𝜀 + 3.0913 × 10−2 = 0
The solutions for the equation above are :
𝜀 = 2.1125
𝜀 = 0.0151
It is impossible to get the value of 𝜀 more than 1, so we conclude that 𝜀1 = 0.0151.
The mole fraction of each spesi when the equilibrium achieved is :
0.0151
𝑦𝐶2 𝐻5 𝑂𝐻 = 2−0.0151 = 0.0076
1−0.0151
𝑦𝐶2 𝐻4 = 2−0.0151 = 0.4692
1−0.0151
𝑦𝐻2 𝑂 = 2−0.0151 = 0.4692

Calculation of 𝜺𝟐
𝐶2 𝐻4 (𝑔) + 𝐻2 𝑂(𝑔) → 𝐶2 𝐻5 𝑂𝐻(𝑔)
𝑛𝐶2 𝐻5 𝑂𝐻 = 𝜀
𝑛𝐶2 𝐻4 = 1 − 𝜀 ∑ = 12 − 𝜀
𝑛𝐻2 𝑂 = 1 − 𝜀
𝑛𝑖𝑛𝑒𝑟𝑡 = 10
K at 200oC, 𝐾 ′ = 3.0913 × 10−2

The addition of the inert gas will change the equilibrium state :
Then,
𝜀
𝑦𝐶2 𝐻5 𝑂𝐻 = 12−𝜀
1−𝜀
𝑦𝐶2 𝐻4 = 12−𝜀
𝑜𝑛 −𝜀
𝑦𝐻2 𝑂 = 12−𝜀

(𝑦𝐶2 𝐻5 𝑂𝐻 )
𝐾= = 3.0913 × 10−2
(𝑦𝐶2 𝐻4 ). (𝑦𝐻2 𝑂 )
𝜀
(12 − 𝜀 )
𝐾= = 3.0913 × 10−2
1−𝜀 1−𝜀
(12 − 𝜀 ) (12 − 𝜀 )

𝜀(12 − 𝜀 )
= 3.0913 × 10−2
(1 − 𝜀 ). (1 − 𝜀 )
12𝜀 − 𝜀 2 = 3.0913 × 10−2 (1 − 2𝜀 − 𝜀 2 )
12𝜀 − 𝜀 2 = 3.0913 × 10−2 − 6.1826 × 10−2 𝜀 − 3.0913 × 10−2 𝜀 2
0.9691𝜀 2 − 12.0618𝜀 + 3.0913 × 10−2 = 0

The solutions for the equation above are :


𝜀 = 12.444
𝜀 = 2.563 × 10−3
It is impossible to get the value of 𝜀 more than 1, so we conclude that 𝜀2 = 2.563 × 10−3 .
The mole fraction of each spesi when the equilibrium achieved is :
2.563×10−3
𝑦𝐶2 𝐻5 𝑂𝐻 = 12−2.563×10−3 = 2.14 × 10−4
1−2.563×10−3
𝑦𝐶2 𝐻4 = 12−2.563×10−3 = 0.08314
1−2.563×10−3
𝑦𝐻2 𝑂 = 12−2.563×10−3 = 0.08314
10
𝑦𝑖𝑛𝑒𝑟𝑡 = 12−2.563×10−3 = 0.8335

The effect of the addtional of the inert gas will shift the equilibrium to the reactant side
(𝜀2 < 𝜀1 ), which have the same effect if we decrease the system pressure (which will shift
the equilibrium to the side which have the bigger total reaction coefficients : in this case the
reactant side).