Youngsub Lim

Assistant Professor
Naval Architecture and Ocean Engineering
Seoul National University, S. Korea

414.271 해양 열/전기 기초 2016 봄 Exam 2

You can solve the problems in any order you want.

There are various ways to answer the questions. Any one is OK, if it is reasonable.
The trivial difference in the number is not important.
If the procedure is correct, you will get a partial score even though the number is not correct.
A unit must be specified in your final answer.
You can assume what you need if you think it is necessary.

1. Answer the questions

(a) Explain the equilibrium
(b) Explain the degree of freedom. What happened when the degree of freedom is
smaller than zero?
(c) Explain the van der Waals forces.
𝝏𝒔 𝒄𝑷
(d) Show (𝝏𝑻) =
𝑷 𝑻
(e) Explain the meaning of Joule-Thompson coefficient>0
(f) Explain the chemical potential.
(g) Explain why the molar Gibbs energy has a same meaning with chemical
potential in a pure substance.
(h) Explain the “equal area rule” for a cubic equations of state and verify it.
(i) Derive the Clausius-Clapeyron equation and explain the three assumption
used to derive it
(j) Explain why the partial molar Gibbs energy has a same meaning with
chemical potential in a mixture substance.

2. JT expansion
You are calculating an outlet temperature when you expand nitrogen gas through
Joule-Thomson valve from T1=-120℃, P1=100 bar to P2=1 bar by using RK-EOS.
Answer the question.
𝑹𝑻 𝒂
𝐑𝐊𝐄𝐎𝐒: 𝑷 = −
𝒗 − 𝒃 √𝑻𝒗(𝒗 + 𝒃)
(a) Calculate coefficient 𝒂, 𝒃 of RK-EOS for nitrogen.
𝟎. 𝟒𝟐𝟕𝟒𝟖𝑹𝟐 𝑻𝟐.𝟓
𝒄 𝟎. 𝟎𝟖𝟔𝟔𝟒𝑹𝑻𝒄
𝒂= , 𝒃=
𝑷𝒄 𝑷𝒄
 Youngsub Lim
Assistant Professor
Naval Architecture and Ocean Engineering
Seoul National University, S. Korea
From the steam table A for nitrogen,

𝑻𝒄 = 𝟏𝟐𝟔. 𝟐 [𝐊], 𝑷𝒄 = 𝟑𝟑. 𝟖𝟒 [𝐛𝐚𝐫]

And the universal gas constant is:

𝑹 = 𝟖. 𝟑𝟏𝟒 [𝐉⁄𝐦𝐨𝐥 ∙ 𝐊]

Therefore,
𝟎. 𝟒𝟐𝟕𝟒𝟖𝑹𝟐 𝑻𝟐.𝟓
𝒄 𝟏
𝒂= = 𝟏. 𝟓𝟔𝟐 [𝐉 ∙ 𝐊 𝟐 ∙ 𝐦𝟑 ⁄𝐦𝐨𝐥𝟐 ]
𝑷𝒄

𝟎. 𝟎𝟖𝟔𝟔𝟒𝑹𝑻𝒄
𝒃= = 𝟐. 𝟔𝟖 × 𝟏𝟎−𝟓 [𝐦𝟑 ⁄𝐦𝐨𝐥]
𝑷𝒄

(b) Express the RK-EOS as a cubic equation form of 𝒗 with 𝑷, 𝑻, 𝒂, 𝒃.

Multiply 𝑣(𝑣 + 𝑏)(𝑣 − 𝑏) to both sides

𝑎
𝑃𝑣(𝑣 + 𝑏)(𝑣 − 𝑏) = 𝑅𝑇𝑣(𝑣 + 𝑏) − (𝑣 − 𝑏)
√𝑇

Rearrange the formula about molar volume, 𝑣, then we obtain:

𝒂 𝒂𝒃
𝑷𝒗𝟑 − (𝑹𝑻)𝒗𝟐 + (−𝑷𝒃𝟐 − 𝑹𝑻𝒃 + )𝒗 − =𝟎
√𝑻 √𝑻

(c) The results of (b) can be expressed:

𝑎̅𝑣 3 + 𝑏̅ 𝑣 2 + 𝑐̅𝑣 + 𝑑̅ = 0
Decide 𝒂 ̅, 𝒄̅, 𝒅
̅, 𝒃 ̅ for 𝒗 in (b) and calculate the molar volume of stream 1.
You can use the cubic equation solver in your calculator. If you cannot use it,
you can solve it by using:
𝒒𝟐 𝒑𝟑
When + 𝟐𝟕 ≥ 𝟎
𝟒

3
𝑞 𝑞 2 𝑝3 3 𝑞 𝑞 2 𝑝3 𝑏̅
𝑣 = √− + √ + + √− − √ + −
2 4 27 2 4 27 3𝑎̅

𝒒𝟐 𝒑𝟑
When + 𝟐𝟕 < 𝟎
𝟒
𝒑 𝟏 𝟑𝒒 𝟑 𝟐 ̅
𝒃
𝒗𝒌 = 𝟐√− 𝐜𝐨𝐬 ( 𝐚𝐫𝐜𝐜𝐨𝐬 ( √− ) + 𝒌𝝅) − , 𝒌 = 𝟎, 𝟏, 𝟐
𝟑 𝟑 𝟐𝒑 𝒑 𝟑 𝟑𝒂̅

Where
 Youngsub Lim
Assistant Professor
Naval Architecture and Ocean Engineering
Seoul National University, S. Korea
−𝑏̅ 2 + 3𝑎̅𝑐̅ 2𝑏̅ 3 − 9𝑎̅𝑏̅𝑐̅ + 27𝑎̅2 𝑑̅
𝑝=( ), 𝑞=
3𝑎̅2 27𝑎̅3

With the formula from question 2.(b),

𝑎̅ = 𝑃 = 107
𝑏̅ = −(𝑅𝑇) = −1272
𝑎
𝑐̅ = (−𝑃𝑏 2 − 𝑅𝑇𝑏 + ) = 8.49 × 10−2
√𝑇
𝑎𝑏
𝑑̅ = − = −3.39 × 10−6
√𝑇

By solving the cubic equation, only one real root is obtained as:
𝒗 = 𝟕. 𝟕𝟒 × 𝟏𝟎−𝟓 [𝐦𝟑 ⁄𝐦𝐨𝐥]

(d) Show the enthalpy departure function from RK-EOS can be written as:
3𝑎 𝑣
∆ℎ𝑑𝑒𝑝
𝑇,𝑃 = 𝑃𝑣 − 𝑅𝑇 + ln
2𝑏√𝑇 𝑣+𝑏

𝑃
𝑑𝑒𝑝 𝜕𝑣
∆ℎ 𝑇,𝑃 = ∫ 𝑣 − 𝑇 ( ) 𝑑𝑃
𝑃𝑙𝑜𝑤 𝜕𝑇 𝑃
𝑃 𝑃
𝜕𝑣
=∫ 𝑣𝑑𝑃 − ∫ 𝑇 ( ) 𝑑𝑃
𝑃𝑙𝑜𝑤 𝑃𝑙𝑜𝑤 𝜕𝑇 𝑃
𝑣𝑃 𝑣 𝑃
𝜕𝑣
= ∫ 𝑑(𝑣𝑃) − ∫ 𝑃𝑑𝑣 − ∫ 𝑇 ( ) 𝑑𝑃
𝑅𝑇 𝑣∞ 𝑃𝑙𝑜𝑤 𝜕𝑇 𝑃
𝜕𝑇 𝜕𝑃 𝜕𝑣
( ) ( ) ( ) = −1
𝜕𝑃 𝑣 𝜕𝑣 𝑇 𝜕𝑇 𝑃

At constant temperature,
𝜕𝑇 𝑑𝑃 𝜕𝑣
( ) ( ) = −1
𝜕𝑃 𝑣 𝑑𝑣 𝜕𝑇 𝑃
𝜕𝑣 𝜕𝑃
( ) 𝑑𝑃 = − ( ) 𝑑𝑣
𝜕𝑇 𝑃 𝜕𝑇 𝑣

Apply the cyclic rule

 Youngsub Lim
Assistant Professor
Naval Architecture and Ocean Engineering
Seoul National University, S. Korea
𝑣
𝑑𝑒𝑝 𝜕𝑃
∆ℎ 𝑇,𝑃 = 𝑃𝑣 − 𝑅𝑇 + ∫ [𝑇 ( ) − 𝑃] 𝑑𝑣
𝑣∞ 𝜕𝑇 𝑣

With RK EOS,
𝜕𝑃 𝑅 𝑎
( ) = + 3/2
𝜕𝑇 𝑣 𝑣 − 𝑏 2𝑇 𝑣(𝑣 + 𝑏)
𝜕𝑃 𝑅 𝑎 𝑅𝑇 𝑎 3𝑎
𝑇( ) −𝑃 = 𝑇( + 3/2 )−( − )=
𝜕𝑇 𝑣 𝑣 − 𝑏 2𝑇 𝑣(𝑣 + 𝑏) 𝑣 − 𝑏 √𝑇𝑣(𝑣 + 𝑏) 2√𝑇𝑣(𝑣 + 𝑏)
𝑣
𝑑𝑒𝑝 𝜕𝑃 3𝑎 𝑣 1
∆ℎ 𝑇,𝑃 = 𝑃𝑣 − 𝑅𝑇 + ∫ [𝑇 ( ) − 𝑃] 𝑑𝑣 = 𝑃𝑣 − 𝑅𝑇 + ∫ [ ] 𝑑𝑣
𝑣∞ 𝜕𝑇 𝑣 2√𝑇 𝑣∞ 𝑣(𝑣 + 𝑏)
𝑣
3𝑎 1 1
= 𝑃𝑣 − 𝑅𝑇 + ∫ [ − ] 𝑑𝑣
2𝑏√𝑇 𝑣∞ 𝑣 (𝑣 + 𝑏)
3𝑎
= 𝑃𝑣 − 𝑅𝑇 + [ln 𝑣 − ln(𝑣 + 𝑏)]𝑣𝑣∞
2𝑏√𝑇
3𝑎
= 𝑃𝑣 − 𝑅𝑇 + [ln 𝑣 − ln 𝑣∞ − ln(𝑣 + 𝑏) + ln(𝑣∞ + 𝑏)]
2𝑏√𝑇
3𝑎 𝑣 𝑣∞ + 𝑏
= 𝑃𝑣 − 𝑅𝑇 + [ln + ln ]
2𝑏√𝑇 𝑣+𝑏 𝑣∞
3𝑎 𝑣
= 𝑃𝑣 − 𝑅𝑇 + ln
2𝑏√𝑇 𝑣+𝑏

𝒅𝒆𝒑 𝟑𝒂 𝒗
∴ ∆𝒉𝑻,𝑷 = 𝑷𝒗 − 𝑹𝑻 + 𝐥𝐧
𝟐𝒃√𝑻 𝒗+𝒃

(e) Calculate molar enthalpy of the input stream 1 by using enthalpy departure
function. Reference temperature is 25℃

𝑑𝑒𝑝
ℎ1 = ℎ𝑖𝑔 + Δℎ 𝑇,𝑃
𝑇𝑟𝑒𝑓 = 25 + 273 = 298 [K]

From the heat capacity table at appendix A for nitrogen,

𝐴 = 3.280, 𝐵 = 0.593 × 10−3 , and 𝐷 = 0.04 × 105

𝑻𝟏 𝑻𝟏
𝑩 𝟐 𝑫 𝟏𝟓𝟑
𝒉𝒊𝒈 = ∫ 𝒄𝑷 𝒅𝑻 = 𝑹 ∫ 𝑨 + 𝑩𝑻 + 𝑫𝑻−𝟐 𝒅𝑻 = 𝑹 [𝑨𝑻 + 𝑻 − ]
𝑻𝒓𝒆𝒇 𝑻𝒓𝒆𝒇 𝟐 𝑻 𝟐𝟗𝟖
= −𝟒𝟐𝟐𝟏 [𝐉⁄𝐦𝐨𝐥]
 Youngsub Lim
Assistant Professor
Naval Architecture and Ocean Engineering
Seoul National University, S. Korea

𝑑𝑒𝑝 3𝑎 𝑣1
∆ℎ 𝑇,𝑃 = 𝑃1 𝑣1 − 𝑅𝑇1 + ln = −2703 [J⁄mol]
2𝑏√𝑇1 𝑣1 + 𝑏
𝑑𝑒𝑝
ℎ1 = ℎ𝑖𝑔 + Δℎ 𝑇,𝑃 = −4221 − 2703 = −6924 [J⁄mol] = −6.92 [k J⁄mol]

(f) Calculate molar volume of saturated liquid and saturated vapor for nitrogen at
P=1 bar.

From the Antoine Equation,

𝐵
ln(𝑃 𝑠𝑎𝑡 [bar]) = 𝐴 −
𝑇[𝐾] + 𝐶
𝐴 = 8.3340, 𝐵 = 588.72, and 𝐶 = −6.60
𝐵
𝑇 𝑠𝑎𝑡 = −𝐶 + = 77.2 [K]
− ln(𝑃 𝑠𝑎𝑡 ) + 𝐴

With this saturation temperature, we can arrange RK EOS and that is:
𝑎 𝑎𝑏
𝑃𝑣 3 − (𝑅𝑇)𝑣 2 + (−𝑃𝑏 2 − 𝑅𝑇𝑏 + )𝑣 − =0
√𝑇 √𝑇
𝑎̅ = 𝑃 = 105
𝑏̅ = −(𝑅𝑇) = −642
𝑎
𝑐̅ = (−𝑃𝑏 2 − 𝑅𝑇𝑏 + ) = 1.604 × 10−1
√𝑇
𝑎𝑏
𝑑̅ = − = −4.78 × 10−6
√𝑇

By solving the cubic EOS, we can obtain 3 real roots. However, as we know, the greatest real root is
the molar volume of vapor phase, the smallest real root is for the liquid phase, and the middle one
does not stands for any physical property. Therefore, the molar volumes of saturated liquid and
vapor are:

𝒗𝒔𝒂𝒕
𝒍𝒊𝒒 = 𝟑. 𝟒𝟓 × 𝟏𝟎
−𝟓
[𝐦𝟑 ⁄𝐦𝐨𝐥]
𝒗𝒔𝒂𝒕
𝒗𝒂𝒑 = 𝟔. 𝟏𝟔 × 𝟏𝟎
−𝟑
[𝐦𝟑 ⁄𝐦𝐨𝐥]

(g) Calculate molar enthalpy of saturated liquid and saturated vapor for nitrogen
at P=1 bar.
 Youngsub Lim
Assistant Professor
Naval Architecture and Ocean Engineering
Seoul National University, S. Korea

𝒊𝒈
𝑻𝟐 𝑻𝟐
𝑩 𝟐 𝑫 𝟕𝟕.𝟐
𝒉𝟐 = ∫ 𝒄𝑷 𝒅𝑻 = 𝑹 ∫ 𝑨 + 𝑩𝑻 + 𝑫𝑻−𝟐 𝒅𝑻 = 𝑹 [𝑨𝑻 + 𝑻 − ]
𝑻𝒓𝒆𝒇 𝑻𝒓𝒆𝒇 𝟐 𝑻 𝟐𝟗𝟖
= −𝟔𝟓𝟒𝟑 [𝐉⁄𝐦𝐨𝐥]

𝑙𝑖𝑞
𝑑𝑒𝑝 𝑙𝑖𝑞 3𝑎 𝑣2
∆ℎ𝑙𝑖𝑞 = 𝑃2 𝑣2 − 𝑅𝑇2 + ln 𝑙𝑖𝑞
= −6354 [J⁄mol]
2𝑏√𝑇2 𝑣2 + 𝑏
𝑙𝑖𝑞 𝑖𝑔 𝑑𝑒𝑝
ℎ2 = ℎ2 + Δℎ𝑙𝑖𝑞 = −6543 − 6354 = −12900 [J⁄mol] = −12.90 [k J⁄mol]

𝑣𝑎𝑝
𝑑𝑒𝑝 𝑣𝑎𝑝 3𝑎 𝑣2
∆ℎ𝑣𝑎𝑝 = 𝑃2 𝑣2 − 𝑅𝑇2 + ln 𝑣𝑎𝑝 = −69.1 [J⁄mol]
2𝑏√𝑇2 𝑣2 +𝑏
𝑣𝑎𝑝 𝑖𝑔 𝑑𝑒𝑝
ℎ2 = ℎ2 + Δℎ𝑙𝑖𝑞 = −6543 − 69.1 = −6612 [J⁄mol] = −6.61 [k J⁄mol]

𝒍𝒊𝒒 𝒗𝒂𝒑
∴ 𝒉𝟐 = −𝟏𝟐. 𝟗𝟎 [𝐤 𝐉⁄𝐦𝐨𝐥] and 𝒉𝟐 = −𝟔. 𝟔𝟏 [𝐤 𝐉⁄𝐦𝐨𝐥]

(h) Calculate vapor fraction of stream 2.

Since JT expansion is an isenthalpic process:

ℎ1 = ℎ2 = −6.92 [k J⁄mol]

By applying lever rule:

ℎ2 = (1 − 𝑥)ℎ𝑣 + 𝑥ℎ𝑙

𝒉𝟐 − 𝒉𝒍
∴𝒙= = 𝟎. 𝟗𝟓𝟎
𝒉𝒗 − 𝒉𝒍

3. Separation of propane
You are designing a separation process to separate
propane from NG (natural gas) feed stream. When the
NG feed is assumed as an ideal mixture of 80% methane
and 20% propane and the flow rate is 100 mol/s, answer
the question.

(a) Calculate dew point and bubble point of the

methane 80%, propane 20% mixture at 1 bar.
 Youngsub Lim
Assistant Professor
Naval Architecture and Ocean Engineering
Seoul National University, S. Korea

1) Bubble point
𝑦1 𝑃 = 𝑥1 𝑃1𝑠𝑎𝑡
𝑦2 𝑃 = 𝑥2 𝑃2𝑠𝑎𝑡
𝑃 = 1 = 𝑥1 𝑃1𝑠𝑎𝑡 + 𝑥2 𝑃2𝑠𝑎𝑡 = 0.8𝑃1𝑠𝑎𝑡 + 0.2𝑃2𝑠𝑎𝑡
T = 114K
2) Dew point
𝑦1 𝑃
𝑥1 =
𝑃1𝑠𝑎𝑡
𝑦1 𝑃
𝑥2 =
𝑃1𝑠𝑎𝑡
𝑦1 𝑦2 0.8 0.2
1 = 𝑃( 𝑠𝑎𝑡 + 𝑠𝑎𝑡 ) = 1 ∗ ( 𝑠𝑎𝑡 + 𝑠𝑎𝑡 )
𝑃1 𝑃2 𝑃1 𝑃2
T = 200K

(b) When the separation pressure and temperature are 1 bar, -100℃, calculate the
flow rate and methane composition of the vapor and liquid stream.

𝑻 = −𝟏𝟎𝟎 + 𝟐𝟕𝟑 = 𝟏𝟕𝟑𝑲

𝑷𝒔𝒂𝒕
𝟏 = 𝟐𝟒. 𝟑𝒃𝒂𝒓 , 𝑷𝒔𝒂𝒕
𝟐 = 𝟎. 𝟎𝟐𝟖𝒃𝒂𝒓

𝑦𝑃 = 𝑥𝑃 𝑠𝑎𝑡
𝑥1 𝑃1𝑠𝑎𝑡 𝑥2 𝑃2𝑠𝑎𝑡
𝑦1 = 𝑃
=24.3𝑥1 , 𝑦2 = 𝑃
=0.028𝑥2 ,
𝑥1 𝑃1𝑠𝑎𝑡 𝑥2 𝑃2𝑠𝑎𝑡
1=𝑦1 +𝑦2 = 𝑃
+ 𝑃
=24.3𝑥1 +0.028𝑥2 =24.3𝑥1 +0.028(1-𝑥1 )
𝒙𝟏 = 𝟎. 𝟎𝟒, 𝒙𝟐 = 𝟎. 𝟗𝟔
𝒚𝟏 = 𝟎. 𝟗𝟕𝟐, 𝒚𝟐 = 𝟎. 𝟎𝟐𝟕 (𝒙𝟏 , 𝒚𝟏 만 써도 𝑶𝑲)
𝐹 = 100 = 𝑉 + 𝐿
𝑧1 𝐹 = 𝑦1 𝑉 + 𝑥1 𝐿, 0.8𝐹 = 0.972𝑉 + 0.04𝐿

V=81.5mol,L=18.5mol

(c) Draw a Pxy diagram of methane-propane mixture and mark the result of (b)
on the diagram
 Youngsub Lim
Assistant Professor
Naval Architecture and Ocean Engineering
Seoul National University, S. Korea

Diagram 개형, 𝑃 𝑠𝑎𝑡 표시 (b)표시

(d) When the separation pressure is increased, how the methane composition in
vapor and liquid stream will be changed? Explain by using Pxy diagram.

Liquid stream 의 methane composition 이 급격히 증가. Vapor stream 의 methane composition 이 증가.

4. Fugacity
For PR EOS, the fugacity of pure substance is written as:
 Youngsub Lim
Assistant Professor
Naval Architecture and Ocean Engineering
Seoul National University, S. Korea

𝑷𝒗 𝑷(𝒗 − 𝒃) 𝒂 𝒗 + (𝟏 + √𝟐)𝒃
𝐥𝐧 𝝋 = − 𝟏 − 𝐥𝐧 ( )− 𝐥𝐧 ( )
𝑹𝑻 𝑹𝑻 𝒃𝑹𝑻𝟐√𝟐 𝒗 + (𝟏 − √𝟐)𝒃
𝑹𝑻 𝒂
𝑷= −
𝒗 − 𝒃 𝒗(𝒗 + 𝒃) + 𝒃(𝒗 − 𝒃)
(𝑹𝑻𝒄 )𝟐 𝑹𝑻𝒄
𝒂 = 𝟎. 𝟒𝟓𝟕𝟐𝟒 𝜶, 𝒃 = 𝟎. 𝟎𝟕𝟕𝟖𝟎
𝑷𝒄 𝑷𝒄
𝟐
𝜶 = [𝟏 + 𝜿(𝟏 − √𝑻𝒓 )]
𝜿 = 𝟎. 𝟑𝟕𝟒𝟔𝟒 + 𝟏. 𝟓𝟒𝟐𝟐𝟔𝝎 − 𝟎. 𝟐𝟔𝟗𝟗𝟐𝝎𝟐
(a) Calculate the pressure at T=300 K, v=0.005 m3/mol for propane by using PR
EOS.

From appendix A for propane,

𝑇𝑐 = 370.0 [K], 𝑃𝑐 = 42.44 [bar], and 𝜔 = 0.152
𝜅 = 0.37464 + 1.54226𝜔 − 0.26992𝜔2 = 0.603
2
𝛼 = [1 + 𝜅(1 − √𝑇𝑟 )] = 1.127
(𝑅𝑇𝑐 )2
𝑎 = 0.45724 𝛼 = 1.145
𝑃𝑐
𝑅𝑇𝑐
𝑏 = 0.07780 = 5.64 × 10−5
𝑃𝑐

Using the coefficients, we can directly calculate the PR CEOS and the result is:
𝑹𝑻 𝒂
𝑷= − = 𝟒. 𝟔𝟎 [𝐛𝐚𝐫]
𝒗 − 𝒃 𝒗(𝒗 + 𝒃) + 𝒃(𝒗 − 𝒃)

(b) Calculate the fugacity at T=300 K, v=0.005 m3/mol for propane.

𝑃𝑣 𝑃(𝑣 − 𝑏) 𝑎 𝑣 + (1 + √2)𝑏
ln 𝜑 = − 1 − ln ( )− ln ( ) = −0.0763
𝑅𝑇 𝑅𝑇 𝑏𝑅𝑇2√2 𝑣 + (1 − √2)𝑏
∴ 𝜑 = 0.927
𝑓
Since 𝜑 = , the fugacity at this state is
𝑃

∴ 𝒇 = 𝝋𝑷 = 𝟎. 𝟗𝟐𝟕 × 𝟒. 𝟔 = 𝟒. 𝟐𝟔 [𝐛𝐚𝐫]

(c) Is your resulting fugacity smaller or larger than the pressure? Why?