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August 20,

PROBLEMS ZAID YAHYA 11-CH-74


2013

Chapter 3
Problems
Problem 3.1:

Express the volume expansivity β and isothermal compressibility κ as functions of


density ρ and its partial derivatives. The isothermal compressibility coefficient ( ) of
water at 50 oC and 1 bar is 𝟒𝟒. 𝟏𝟖 ∗ 𝟏𝟎−𝟔 bar-1. To what pressure must water be
compressed at 50 oC to change its density by 1%? Assume that  is independent of P.

Given Data:

1 𝜕𝑉
𝑉𝑜𝑙𝑢𝑚𝑒 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑣𝑖𝑡𝑦 = 𝛽 = ( )
𝑉 𝜕𝑇 𝑃

 Or
1 𝑑𝑉
𝛽= ( ) → (1)
𝑉 𝑑𝑇 𝑃
1 𝜕𝑉
𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝐶𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑖𝑙𝑡𝑦 = 𝜅 = − ( )
𝑉 𝜕𝑃 𝑇
 Or
1 𝑑𝑉
𝜅 = − ( ) → (2)
𝑉 𝑑𝑃 𝑇
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇 = 50 0C
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃1 = 1 𝑏𝑎𝑟
𝜅 = 44.18 ∗ 10−6 𝑏𝑎𝑟 −1
𝑘𝑔
𝐷𝑒𝑛𝑠𝑖𝑡𝑦 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 = 𝜌1 = 1 3
𝑚
𝑘𝑔
𝜌2 = (1 + 1%) 3
𝑚
𝑘𝑔
𝜌2 = 1.01 3
𝑚
𝑃2 =?

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August 20,
PROBLEMS ZAID YAHYA 11-CH-74
2013

Solution:
(a)

 We know that

1
𝜌=
𝑉
1
𝑉=
𝜌
 Put in (1) & (2)

𝑑 1
𝛽 = 𝜌( )
𝑑𝑇 𝜌 𝑃
𝜌 𝑑𝜌
𝛽 = − 2( )
𝜌 𝑑𝑇 𝑃
𝟏 𝒅𝝆
𝜷=− ( ) Proved
𝝆 𝒅𝑻 𝑷
 Now,

𝑑 1
𝜅 = −𝜌 ( )
𝑑𝑃 𝜌 𝑇
𝜌 𝑑𝜌
𝜅= ( )
𝜌2 𝑑𝑃 𝑇
𝟏 𝒅𝝆
𝜿 = 𝝆 (𝒅𝑷) Proved
𝑻
(b)

 As

1 𝑑𝜌
𝜅= ( )
𝜌 𝑑𝑃 𝑇
𝑑𝜌
𝜅𝑑𝑃 =
𝜌

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2013

 Integrating on both sides


𝑃2 𝜌2
𝑑𝜌
𝜅 ∫ 𝑑𝑃 = ∫
𝑃1 𝜌1 𝜌
𝑃 𝜌
𝜅|𝑃|𝑃21 = |ln 𝜌|𝜌21
𝜅(𝑃2 − 𝑃1 ) = (ln 𝜌2 − ln 𝜌1 )
𝜌2
𝜅(𝑃2 − 𝑃1 ) = 𝑙𝑛
𝜌1
 Putting values

44.18 ∗ 10−6 ln 1.01


(𝑃2 − 1) =
𝑏𝑎𝑟 1
𝑏𝑎𝑟
𝑃2 − 1 = 0.00995 ∗
44.18 ∗ 10−6
𝑃2 = (225.22 + 1)𝑏𝑎𝑟
𝑷𝟐 = 𝟐𝟐𝟔. 𝟐𝟐 𝒃𝒂𝒓 Answer

Problem 3.2:

Generally, volume expansivity β and isothermal compressibility κ depend on T and P.


Prove that

𝝏𝜷 𝝏𝜿
( ) = −( )
𝝏𝑷 𝑻 𝝏𝑻 𝑷

Solution:
 We know that

1 𝜕𝑉
𝑉𝑜𝑙𝑢𝑚𝑒 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑣𝑖𝑡𝑦 = 𝛽 = ( )
𝑉 𝜕𝑇 𝑃
 Since 𝛽 is very small
1 𝜕𝑉
𝑉= ( ) → (1)
𝜕𝛽 𝜕𝑇 𝑃
1 𝜕𝑉
𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝐶𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑖𝑙𝑡𝑦 = 𝜅 = − ( )
𝑉 𝜕𝑃 𝑇
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August 20,
PROBLEMS ZAID YAHYA 11-CH-74
2013

 Since κ is very small


1 𝜕𝑉
𝑉=− ( )
𝜕𝜅 𝜕𝑃 𝑇
1 𝜕𝑉 1 𝜕𝑉
( ) =− ( )
𝜕𝛽 𝜕𝑇 𝑃 𝜕𝜅 𝜕𝑃 𝑇
1 1 1 1
( ) 𝜕𝑉 = − ( ) 𝜕𝑉
𝜕𝛽 𝜕𝑇 𝑃 𝜕𝜅 𝜕𝑃 𝑇
𝜕𝜅 𝜕𝛽
−( ) =( )
𝜕𝑇 𝑃 𝜕𝑃 𝑇
𝝏𝜷 𝝏𝜿
( ) = −( ) Proved
𝝏𝑷 𝑻 𝝏𝑻 𝑷

Problem 3.3:

The Tait equation for liquids is written for an isotherm as:


𝑨𝑷
𝑽 = 𝑽𝟎 (𝟏 − )
𝑩+𝑷
Where V is specific or molar volume, Vo is the hypothetical molar or specific volume at
P = 0 and A & B are positive constant. Find an expression for the isothermal
compressibility consistent with this equation.

Solution:
 We Know That,
1 𝜕𝑉
𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝐶𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑖𝑙𝑡𝑦 = 𝜅 = − ( ) → (1)
𝑉 𝜕𝑃 𝑇
 Given that
𝐴𝑃
𝑉 = 𝑉0 (1 − )
𝐵+𝑃

 Where
 V0 = Hypothetical molar/specific volume at zero pressure, so it is constant
 V = Molar/specific volume
 Now,
𝐴𝑃
𝑉 = 𝑉𝑜 − V
𝐵+𝑃 o

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August 20,
PROBLEMS ZAID YAHYA 11-CH-74
2013

𝐴𝑃
𝑉 − 𝑉𝑜 = − 𝑉
𝐵+𝑃 𝑜
𝑉 − 𝑉𝑜 𝐴𝑃
=−
𝑉𝑜 𝐵+𝑃
 Differentiate w.r.t Pressure
1 𝜕 𝜕 𝐴𝑃
(𝑉 − 𝑉𝑜 ) = − ( )
𝑉𝑜 𝜕𝑃 𝜕𝑃 𝐵 + 𝑃
1 𝜕𝑉 𝐴(𝐵 + 𝑃) − 𝐴𝑃(1)
( − 0) = − [ ]
𝑉𝑜 𝜕𝑃 (𝐵 + 𝑃)2

1 𝜕𝑉 𝐴𝐵 + 𝐴𝑃 − 𝐴𝑃
− ( )=
𝑉𝑜 𝜕𝑃 (𝐵 + 𝑃)2
1 𝜕𝑉 𝐴𝐵
− ( )=
𝑉𝑜 𝜕𝑃 (𝐵 + 𝑃)2
 Since, Temperature is constant
 Therefore,
1 𝜕𝑉 𝐴𝐵
− ( ) =
𝑉𝑜 𝜕𝑃 𝑇 (𝐵 + 𝑃)2
 Or, From (1)

𝑨𝑩
𝜿=( Proved
𝑩+𝑷)𝟐

Problem 3.4:

For liquid water the isothermal compressibility is given by:


𝒄
𝜿=
𝑽(𝑷 + 𝒃)
Where c & b are functions of temperature only if 1 kg of water is compressed
isothermally & reversibly from 1 bar to 500 bars at 60 oC, how much work is required?
At 60 oC, b=2700 bars and c = 0.125 cm3 g-1

Given Data:

𝑐
𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑖𝑙𝑖𝑡𝑦 = 𝜅 =
𝑉 (𝑃 + 𝑏)
𝑀𝑎𝑠𝑠 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 = 𝑚 = 1 𝑘𝑔

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August 20,
PROBLEMS ZAID YAHYA 11-CH-74
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𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃1 = 1 𝑏𝑎𝑟
𝑃2 = 500 𝑏𝑎𝑟𝑠
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇 = 60 0C

𝑏 = 2700 𝑏𝑎𝑟𝑠
𝑐 = 0.125 𝑐𝑚3 ⁄𝑔
𝑊𝑜𝑟𝑘 = 𝑊 =?
Solution:
 We know that

𝑊 = − ∫ 𝑃𝑑𝑉 → (1)

𝑐
𝜅= → (2)
𝑉(𝑃 + 𝑏)
 Also

1 𝑑𝑉
𝜅 = − ( ) → (3)
𝑉 𝑑𝑃 𝑇

 Comparing (2) & (3)


1 𝑑𝑉 𝑐
− =
𝑉 𝑑𝑃 𝑉(𝑃+𝑏)
𝑐 𝑑𝑃
−𝑑𝑉 =
𝑃+𝑏
 Put in (1)
𝑐 𝑑𝑃
𝑊 = − ∫ −𝑃
𝑃+𝑏
𝑃2
𝑃
𝑊 = 𝑐∫ 𝑑𝑃
𝑃1 𝑃+𝑏
𝑃2
𝑃+𝑏−𝑏
𝑊 = 𝑐∫ 𝑑𝑃
𝑃1 𝑃+𝑏
𝑃2 𝑃2
𝑃+𝑏 𝑏
𝑊 = 𝑐∫ 𝑑𝑃 − 𝑐 ∫ 𝑑𝑃
𝑃1 𝑃 + 𝑏 𝑃1 𝑃 + 𝑏

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August 20,
PROBLEMS ZAID YAHYA 11-CH-74
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𝑃2 𝑃2
1
𝑊 = 𝑐 ∫ 𝑑𝑃 − 𝑏𝑐 ∫ 𝑑𝑃
𝑃1 𝑃1 𝑃+𝑏
𝑃 𝑃
𝑊= 𝑐|𝑃|𝑃21 − 𝑏𝑐|𝑙𝑛(𝑃 + 𝑏)|𝑃21
𝑊 = 𝑐(𝑃2 − 𝑃1 ) − 𝑏𝑐[𝑙𝑛(𝑃2 + 𝑏) − 𝑙𝑛(𝑃1 + 𝑏)]
𝑃2 + 𝑏
𝑊 = 𝑐(𝑃2 − 𝑃1 ) − 𝑏𝑐 [𝑙𝑛 ]
𝑃1 + 𝑏
 Putting values

𝑐𝑚3 𝑐𝑚3 500+2700


𝑊 = 0.125 ∗ (500 − 1)𝑏𝑎𝑟 − 2700𝑏𝑎𝑟 ∗ 0.125 ∗ 𝑙𝑛
𝑔 𝑔 1+2700
3 3
𝑐𝑚 ∗ 𝑏𝑎𝑟 𝑐𝑚 ∗ 𝑏𝑎𝑟
𝑊 = 62.375 − 57.216
𝑔 𝑔
𝑐𝑚3 ∗ 𝑏𝑎𝑟
𝑊 = 5.16
𝑔
3
𝑐𝑚 ∗ 𝑏𝑎𝑟 1𝑚3 101325 𝑁 𝑱
𝑊 = 5.16 ∗ ∗ ∗
𝒈 1003 𝑐𝑚3 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 𝑁𝑚
𝑱
𝑾 = 𝟎. 𝟓𝟏𝟔 Answer
𝒈

Problem 3.5:

Calculate the reversible work done in compressing 1 ft3 of mercury at a constant


temperature of 32F from 1(atm) to 3,000(atm). The isothermal compressibility of
mercury at 32F is:
κ/(atm)-1 = 3.9 x 10-6 - 0.1 x10-9P(atm)

Given Data:

𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 = 𝑊 =?
𝑉𝑜𝑙𝑢𝑚𝑒 = 𝑉 = 1 𝑓𝑡 3
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇 = 32 𝐹
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃1 = 1 𝑎𝑡𝑚
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃2 = 3000 𝑎𝑡𝑚
𝜅⁄𝑎𝑡𝑚−1 = 3.9 ∗ 10−6 − 0.1 ∗ 10−9 𝑃(𝑎𝑡𝑚)

 Where

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August 20,
PROBLEMS ZAID YAHYA 11-CH-74
2013

 Term, 3.9*10-6 has unit of atm-1 & 0.1*10-9 has units of atm-2

Solution:
 We know that, work done for a reversible process is

𝑊 = − ∫ 𝑃𝑑𝑉 → (1)

 Also

1 𝑑𝑉
𝜅=− ( )
𝑉 𝑑𝑃 𝑇
𝑑𝑉 = −κVdP
 Put in (1),

𝑊 = − ∫ 𝑃 (−𝜅𝑉𝑑𝑝)
𝑃2
𝑊 = 𝑉 ∫ 𝜅 𝑃 𝑑𝑃
𝑃1

𝑃2
𝑊 = 𝑉 ∫ (3.9 ∗ 10−6 − 0.1 ∗ 10−9 𝑃)𝑃 𝑑𝑃
𝑃1
𝑃2 𝑃2
𝑊 = 𝑉 ∫ 3.9 ∗ 10 𝑃 𝑑𝑃 − 𝑉 ∫ 0.1 ∗ 10−9 𝑃2 𝑑𝑃
−6
𝑃1 𝑃1
3000 3000
−6 −9
𝑊 = 3.9 ∗ 10 𝑉 ∫ 𝑃 𝑑𝑃 − 0.1 ∗ 10 𝑉 ∫ 𝑃2 𝑑𝑃
1 1

3000 3000
𝑃2
−6 −9
𝑃3
𝑊 = 3.9 ∗ 10 𝑉 | | − 0.1 ∗ 10 𝑉 | |
2 1 3 1
1.95 ∗ 10−6 ∗ 1 𝑓𝑡 3 2 2 2
3.333 ∗ 10−11 ∗ 1 𝑓𝑡 3
𝑊= (3000 − 1 )𝑎𝑡𝑚 −
𝑎𝑡𝑚 𝑎𝑡𝑚2
∗ (30003 − 13 ) 𝑎𝑡𝑚3

𝑊 = (17.55 − 0.8991)𝑎𝑡𝑚 ∗ 𝑓𝑡 3
𝑾 = 𝟏𝟔. 𝟔𝟓 𝒂𝒕𝒎 ∗ 𝒇𝒕𝟑 Answer
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Problem 3.6:

Five kilograms of liquid carbon tetrachloride undergo a mechanically reversible,


isobaric change of state at 1 bar during which the temperature change from 0oC to 20oC.
Determine ΔVt, W, Q, and ΔUt. The properties for liquid carbon tetrachloride at 1 bar &
0oC may be assumed independent of temperature: β = 1.2 x 10-3 K-1 Cp = 0.84 kJ kg-1 K-
1, ρ = 1590 kg m-3

Given Data:

𝑀𝑎𝑠𝑠 = 𝑚 = 5 𝑘𝑔
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃 = 1 𝑏𝑎𝑟
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇1 = 0 0C

𝑇1 = 273.15 𝐾

𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇2 = 20 0C
𝑇2 = (20 + 273.15)𝐾
𝑇2 = 293.15 𝐾
𝛽 = 1.2 ∗ 10−3 𝐾 −1
𝑘𝐽
𝐶𝑃 = 0.84
𝑘𝑔 ∗ 𝐾
𝑘𝑔
𝜌 = 1590 3
𝑚
𝑡
∆𝑉 =?
𝑊 =?
𝑄 =?
∆𝑈𝑡 =?

Solution:
 As

1
𝑉=
𝜌
1
𝑉1 =
𝜌1

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1 𝑚3
𝑉1 =
1590 𝑘𝑔
 Also,
 we know that

1 𝑑𝑉
𝑉𝑜𝑙𝑢𝑚𝑒 𝑒𝑥𝑝𝑎𝑛𝑠𝑖𝑣𝑖𝑡𝑦 = 𝛽 = ( )
𝑉 𝑑𝑇 𝑃
1
𝛽𝑑𝑇 = 𝑑𝑉
𝑉
 Integrating on both sides,
𝑇2 𝑉2
𝑑𝑉
𝛽 ∫ 𝑑𝑇 = ∫
𝑇1 𝑉1 𝑉
𝑇 𝑉
𝛽|𝑇| 𝑇21 = |ln 𝑉|𝑉21
𝛽(𝑇2 − 𝑇1 ) = (ln 𝑉2 − ln 𝑉1 )
𝑉2
𝛽(𝑇2 − 𝑇1 ) = 𝑙𝑛
𝑉1
 Putting values
1.2 ∗ 10−3 𝑉2 ∗ 1590𝑘𝑔
∗ (293.15 − 273.15)𝐾 = 𝑙𝑛
𝐾 𝑚3
𝑉2 ∗ 1590𝑘𝑔
𝑒 0.024 =
𝑚3
1.024 𝑚3
𝑉2 = ∗
1590 𝑘𝑔
𝒎𝟑
𝑽𝟐 = 𝟎. 𝟎𝟎𝟎𝟔𝟒𝟒
𝒌𝒈
 Now,

∆𝑉 = 𝑉2 − 𝑉1
1 𝑚3
∆𝑉 = (0.000644 − )
1590 𝑘𝑔
−6
𝑚3
∆𝑉 = 15.28 ∗ 10
𝑘𝑔
 Now, for total volume,
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August 20,
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∆𝑉 𝑡 = ∆𝑉 ∗ 𝑚
𝑡
𝑚3
−6
∆𝑉 = (15.28 ∗ 10 ∗ 5) ∗ 𝑘𝑔
𝑘𝑔
∆𝑽𝒕 = 𝟕. 𝟔𝟑𝟖 ∗ 𝟏𝟎−𝟓 𝒎𝟑 Answer
 Now,
 We know that for a reversible process,

𝑊𝑜𝑟𝑘 𝑑𝑜𝑛𝑒 = 𝑊 = −𝑃∆𝑉 𝑡


101325 𝑁 𝐽 1 𝒌𝑱
𝑊 = −1𝑏𝑎𝑟 ∗ 7.638 ∗ 10−5 𝑚3 ∗ ∗ ∗
1.01325 𝑏𝑎𝑟 ∗ 𝑚2 𝑁𝑚 1000 𝐽
𝑾 = −𝟕. 𝟔𝟑𝟖 ∗ 𝟏𝟎−𝟑 𝒌𝑱 Answer
 Now,
 For a reversible process at constant pressure,we have

𝑄 = ∆𝐻
𝑄 = 𝑚𝐶𝑃 ∆𝑇
𝑘𝐽
𝑄 = 5 𝑘𝑔 ∗ 0.84 ∗ (293.15 − 273.15) 𝐾
𝑘𝑔 ∗ 𝐾
𝑸 = 𝟖𝟒 𝒌𝑱 Answer
 Now,
 According to first law of thermodynamics,
∆𝑈 𝑡 = 𝑄 + 𝑊
∆𝑈 𝑡 = (84 − 7.368 ∗ 10−3 )𝑘𝐽
∆𝑼𝒕 = 𝟖𝟑. 𝟗𝟗 𝒌𝑱 Answer

Problem 3.7:

A substance for which k is a constant undergoes an isothermal, mechanically reversible


process from initial state (P1, V1) to (P2, V2), where V is a molar volume.
a) Starting with the definition of k, show that the path of the process is described by
𝑽 = 𝑨(𝑻)𝒆𝒙𝒑(−𝜿𝑷)
b) Determine an exact expression which gives the isothermal work done on 1 mol of this
constant-k substance.

Solution:

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(a)

 We know that
1 𝑑𝑉
𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑖𝑙𝑡𝑦 = 𝜅 = − ( )
𝑉 𝑑𝑃 𝑇
𝑑𝑉
= −𝜅𝑑𝑃
𝑉
 Integrating on both sides,
𝑑𝑉
∫ = −𝜅 ∫ 𝑑𝑃
𝑉
𝑙𝑛𝑉 = −𝜅𝑃 + 𝑙𝑛𝐴(𝑇)

 Where ln A (T) is constant of integration & A depends on T only


𝑙𝑛𝑉 − 𝑙𝑛𝐴𝑇 = −𝜅𝑃
𝑉
ln = −κP
𝐴(𝑇)
 Taking anti log on both sides,
𝑉
= 𝑒 −𝜅𝑃
𝐴𝑇
V = A(T)𝑒 −𝜅𝑃
 Or
𝑽 = 𝑨(𝑻) 𝒆𝒙𝒑(−𝜿𝑷) Proved

(b)

Work done=W=?
 For a mechanically reversible process, we have,
𝑑𝑊 = −𝑃𝑑𝑉 → (1)
 Using,
𝑑(𝑃𝑉) = 𝑃𝑑𝑉 + 𝑉𝑑𝑃
−𝑃𝑑𝑉 = 𝑉𝑑𝑃 − 𝑑(𝑃𝑉)
 Put in (1)

𝑑𝑊 = 𝑉𝑑𝑃 − 𝑑(𝑃𝑉) → (2)


 We know that
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2013

1 𝑑𝑉
𝐼𝑠𝑜𝑡ℎ𝑒𝑟𝑚𝑎𝑙 𝑐𝑜𝑚𝑝𝑟𝑒𝑠𝑠𝑖𝑏𝑖𝑙𝑡𝑦 = 𝜅 = − ( )
𝑉 𝑑𝑃 𝑇
𝑑𝑉
− = 𝑉𝑑𝑃
𝜅
 Put in (2)

𝑑𝑉
𝑑𝑊 = − − 𝑑(𝑃𝑉)
𝜅
 Integrating on both sides,
1
∫ 𝑑𝑊 = − ∫ 𝑑𝑉 − ∫ 𝑑(𝑃𝑉)
𝜅
1
𝑊 = − Δ𝑉 − Δ(𝑃𝑉)
𝜅
 Since volume changes from V1 to V2 & pressure changes from P1 to P2 ,
 Therefore,

1
𝑊 = − (𝑉2 − 𝑉1 ) − (𝑃2 𝑉2 − 𝑃1 𝑉1 )
𝜅
(𝑽𝟏 − 𝑽𝟐 )
𝑾= + 𝑷𝟏 𝑽𝟏 − 𝑷𝟐 𝑽𝟐 Proved
𝜿

Problem 3.8:

One mole of an ideal gas with CV = 5/2 R, CP = 7/2 R expands from P1 = 8 bars & T1=
600 K to P2 = 1 bar by each of the following path:
a) Constant volume
b) Constant temperature
c) Adiabatically
Assuming mechanical reversibility, calculate W, Q, ∆U, and ∆H for each of the three
processes. Sketch each path in a single PV diagram.

Given Data:

5
𝐶𝑉 = 𝑅
2
7
𝐶𝑃 = 𝑅
2
𝑃1 = 8 𝑏𝑎𝑟
𝑇1 = 600 𝐾
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𝑃2 = 1 𝑏𝑎𝑟
𝑊 =?
𝑄 =?
∆𝑈 =?
∆𝐻 =?

Solution:
(a)

 According to first law of thermodynamics,

∆𝑈 = 𝑄 + 𝑊 → (1)
 For a constant volume process,
𝑊=0
∆𝑈 = 𝐶𝑉 ∆𝑇
 Put in (1)
𝑄 = ∆𝑈 = 𝐶𝑉 ∆𝑇
𝑄 = ∆𝑈 = 𝐶𝑉 (𝑇2 − 𝑇1 ) → (2)
 For T2 , We know that for an ideal gas
𝑇1 𝑇2
=
𝑃1 𝑃2
𝑇1
𝑇2 = ∗ 𝑃2
𝑃1
600 𝐾
𝑇2 = ∗ 1𝑏𝑎𝑟
8 𝑏𝑎𝑟
𝑇2 = 75 𝐾
 Put in (2),
5
𝑄 = ∆𝑈 = 𝑅 (75 − 600) 𝐾
2
5 𝐽
𝑄 = ∆𝑈 = − ∗ 8.314 ∗ 525 𝐾
2 𝑚𝑜𝑙 ∗ 𝐾
𝐽
𝑄 = ∆𝑈 = −10912
𝑚𝑜𝑙
𝒌𝑱
𝑸 = ∆𝑼 = −𝟏𝟎. 𝟗𝟏𝟐 Answer
𝒎𝒐𝒍
 Also
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 For a mechanically reversible process we have,


∆𝐻 = 𝐶𝑃 ∆𝑇
7
∆𝐻 = 𝑅(𝑇2 − 𝑇1 )
2
7 𝐽
∆𝐻 = ∗ 8.314 ∗ (75 − 600)𝐾
2 𝑚𝑜𝑙 ∗ 𝐾
𝐽
∆𝐻 = −15277
𝑚𝑜𝑙
𝒌𝑱
∆𝑯 = −𝟏𝟓. 𝟐𝟕𝟕 Answer
𝒎𝒐𝒍
(b)

 For a constant temperature process,


∆𝑼 = 𝟎
∆𝑯 = 𝟎
 We know that at constant temperature, work done is
𝑃2
𝑊 = 𝑅𝑇1 𝑙𝑛
𝑃1
𝐽 1
𝑊 = 8.314 ∗ 600 𝐾 ∗ ln
𝑚𝑜𝑙∗𝐾 8
𝐽
𝑊 = −10373
𝑚𝑜𝑙
𝒌𝑱
𝑾 = −𝟏𝟎. 𝟑𝟕𝟑 Answer
𝒎𝒐𝒍
 Now, according to first law of thermodynamics,

∆𝑈 = 𝑄 + 𝑊
0=𝑄+𝑊
𝑄 = −𝑊
 Or
𝒌𝑱
𝑸 = 𝟏𝟎. 𝟑𝟕𝟑 Answer
𝒎𝒐𝒍
(c)

 We know that for an adiabatic process


𝑄=0
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 Now, according to first law of thermodynamics,

∆𝑈 = 𝑄 + 𝑊
∆𝑈 = 𝑊 → (1)

∆𝑈 = 𝐶𝑉 ∆𝑇
 Put in (1)
𝑊 = ∆𝑈 = 𝐶𝑉 ∆𝑇
𝑊 = ∆𝑈 = 𝐶𝑉 (𝑇2 − 𝑇1 ) → (2)
 For T2 , We know that for an adiabatic process
(1−𝛾) (1−𝛾)
𝛾 𝛾
𝑇1 𝑃1 = 𝑇2 𝑃2
(1−𝛾)
𝑃1 𝛾
𝑇2 = 𝑇1 ( )
𝑃2
(1−1.4)
8 1.4
𝑇2 = 600 𝐾 ( )
1
𝑇2 = 331.23 𝐾
 Put in (2)
5
𝑊 = ∆𝑈 = 𝑅 ∗ (331.23 − 600) 𝐾
2
5 𝐽
𝑊 = ∆𝑈 = − ∗ 8.314 ∗ 268.77 𝐾
2 𝑚𝑜𝑙 ∗ 𝐾
𝐽
𝑊 = ∆𝑈 = −5586.4
𝑚𝑜𝑙
𝑱
𝑾 = ∆𝑼 = 𝟓. 𝟓𝟖𝟔𝟒 Answer
𝒎𝒐𝒍
 For a mechanically reversible adiabatic process we have
∆𝐻 = 𝐶𝑃 ∆𝑇
7
∆𝐻 = 𝑅 (𝑇2 − 𝑇1 )
2
7 𝐽
∆𝐻 = ∗ 8.314 ∗ (331.23 − 600)𝐾
2 𝑚𝑜𝑙 ∗ 𝐾
𝑱
∆𝑯 = −𝟕. 𝟖𝟐𝟏 Answer
𝒎𝒐𝒍

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Problem 3.9:

An ideal gas initially at 600k and 10 bar undergoes a four-step mechanically reversible
cycle in a closed system. In step 12, pressure decreases isothermally to 3 bars; in step 23,
pressure decreases at constant volume to 2 bars; in step 34, volume decreases at constant
pressure; and in step 41, the gas returns adiabatically to its initial state. Take CP = (7/2)
R and CV = (5/2) R.
a) Sketch the cycle on a PV diagram.
b) Determine (where unknown) both T and P for states 1, 2, 3, and 4.
c) Calculate Q, W, ∆U, and ∆H for each step of the cycle.

Given Data:

𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇1 = 600 𝐾


𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃1 = 10 𝑏𝑎𝑟
7
𝐶𝑃 = 𝑅
2
5
𝐶𝑉 = 𝑅
2

Solution:
(b)

Step 12, an Isothermal process,


 Since
 For an isothermal process, temperature is constant
 Therefore,

𝑻𝟐 = 𝑻𝟏 = 𝟔𝟎𝟎 𝑲
𝑷𝟐 = 𝟑 𝒃𝒂𝒓
 We know that, for an ideal gas

𝑃2 𝑉2 = 𝑅𝑇2
𝑅𝑇2
𝑉2 =
𝑃2

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8.314 ∗ 𝐽 ∗ 600 𝐾 1.01325 𝑏𝑎𝑟 ∗ 𝒎𝟐 𝑁 ∗ 𝒎


𝑉2 = ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 3 𝑏𝑎𝑟 101325 𝑁 𝐽
𝒎𝟑
𝑽𝟐 = 𝟎. 𝟎𝟏𝟔𝟔
𝒎𝒐𝒍
Step 23, an Isochoric process,
 Since
 For an isochoric process, Volume is constant
 Therefore,

𝒎𝟑
𝑽𝟑 = 𝑽𝟐 = 𝟎. 𝟎𝟏𝟔𝟔
𝒎𝒐𝒍
𝑷𝟑 = 𝟐 𝒃𝒂𝒓
 We know that, for an ideal gas

𝑃3 𝑉3 = 𝑅𝑇3
𝑃3 𝑉3
𝑇3 =
𝑅
3
2 𝑏𝑎𝑟 ∗ 0.0166 𝑚 ∗ 𝑚𝑜𝑙 ∗ 𝑲 𝐽 101325 𝑁
𝑇3 = ∗ ∗
𝑚𝑜𝑙 ∗ 8.314 𝐽 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2
𝑻𝟑 = 𝟒𝟎𝟎 𝑲

Step 34, an Isobaric process,


 Since
 For an isobaric process, pressure is constant
 Therefore,

𝑷𝟒 = 𝑷𝟑 = 𝟐 𝒃𝒂𝒓
 For T4 , we will use an adiabatic relation of temperature and pressure
 As

𝑅
𝑇4 𝑃4 𝐶𝑃
=( )
𝑇1 𝑃1
𝑅
𝑃4 𝐶𝑃
𝑇4 = 𝑇1 ( )
𝑃1

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2∗𝑅
2 7𝑅
𝑇4 = 600 𝐾 ∗ ( )
10
𝑻𝟒 = 𝟑𝟕𝟖. 𝟖𝟑 𝑲
 We know that, for an ideal gas

𝑃4 𝑉4 = 𝑅𝑇4
𝑅𝑇4
𝑉4 =
𝑃4
8.314 𝐽 ∗ 378.83 𝐾 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 𝑁𝑚
𝑉4 = ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 2 𝑏𝑎𝑟 101325 𝑁 𝐽
𝒎𝟑
𝑽𝟒 = 𝟎. 𝟎𝟏𝟓𝟕
𝒎𝒐𝒍
Step 41, an adiabatic process,
 Since
 Gas returns to its initial state adiabatically
 Therefore,

𝑻𝟏 = 𝟔𝟎𝟎 𝑲
𝑷𝟏 = 𝟏𝟎 𝒃𝒂𝒓
 We know that, for an ideal gas

𝑃1 𝑉1 = 𝑅𝑇1
𝑅𝑇1
𝑉1 =
𝑃1
8.314 𝐽 ∗ 600 𝐾 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 𝑁𝑚
𝑉1 = ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 10 𝑏𝑎𝑟 101325 𝑁 𝐽
−𝟑
𝒎𝟑
𝑽𝟏 = 𝟒. 𝟗𝟖𝟖 ∗ 𝟏𝟎
𝒎𝒐𝒍
(c)

Step 12, an Isothermal process,


 Since

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 For an isothermal process, temperature is constant


 Therefore

∆𝑼𝟏𝟐 = 𝟎
∆𝑯𝟏𝟐 = 𝟎
 For an isothermal process, we have

𝑃2
𝑄 = −𝑅𝑇1 ln
𝑃1
𝐽 3
𝑄 = −8.314 ∗ 600 𝐾 ∗ ln
𝑚𝑜𝑙 ∗ 𝐾 10
𝐽
𝑄 = 6006
𝑚𝑜𝑙
𝑱
𝑸 = 𝟔. 𝟎𝟎𝟔 ∗ 𝟏𝟎𝟑 Answer
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈12 = 𝑄12 + 𝑊12


0 = 𝑄12 + 𝑊12
𝑊12 = −𝑄12
𝑱
𝑾𝟏𝟐 = −𝟔. 𝟎𝟎𝟔 ∗ 𝟏𝟎𝟑 Answer
𝒎𝒐𝒍

Step 23, an Isochoric process,


 Since
 For an isochoric process, Volume is constant
 Therefore,

𝑾𝟐𝟑 = 𝟎
 At constant volume we have
𝑄23 = ∆𝑈23 = 𝐶𝑉 ∆𝑇
𝑄23 = ∆𝑈23 = 𝐶𝑉 (𝑇3 − 𝑇2 )
5
𝑄23 = ∆𝑈23 = 𝑅(400 − 600)𝐾
2
5 8.314 𝐽
𝑄23 = ∆𝑈23 = ∗ ∗ (−200)𝐾
2 𝑚𝑜𝑙 ∗ 𝐾

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𝐽
𝑄23 = ∆𝑈23 = −4157
𝑚𝑜𝑙
𝑱
𝑸𝟐𝟑 = ∆𝑼𝟐𝟑 = −𝟒. 𝟏𝟓𝟕 ∗ 𝟏𝟎𝟑 Answer
𝒎𝒐𝒍
 We know that

∆𝐻23 = 𝐶𝑃 ∆𝑇
∆𝐻23 = 𝐶𝑃 (𝑇3 − 𝑇2 )
7
∆𝐻23 = 𝑅 (400 − 600)𝐾
2
7 𝐽
∆𝐻23 = ∗ 8.314 ∗ (−200)𝐾
2 𝑚𝑜𝑙 ∗ 𝐾
𝐽
∆𝐻23 = −5820
𝑚𝑜𝑙
𝑱
∆𝑯𝟐𝟑 = −𝟓. 𝟖𝟐 ∗ 𝟏𝟎𝟑 Answer
𝒎𝒐𝒍
Step 34, an Isobaric process,
 Since
 For an isobaric process, pressure is constant
 Therefore, at constant pressure we have,

𝑄34 = ∆𝐻34 = 𝐶𝑃 ∆𝑇
7
𝑄34 = ∆𝐻34 = 𝑅(𝑇4 − 𝑇3 )
2
7 𝐽
𝑄34 = ∆𝐻34 = ∗ 8.314 ∗ (378.83 − 400) 𝐾
2 𝑚𝑜𝑙 ∗ 𝐾
𝑱
𝑸𝟑𝟒 = ∆𝑯𝟑𝟒 = −𝟔𝟏𝟔 Answer
𝒎𝒐𝒍

 For an Isobaric process we have

𝑊34 = −𝑅∆𝑇
𝑊34 = −𝑅(𝑇4 − 𝑇3 )
𝐽
𝑊34 = −8.314 ∗ (378.83 − 400)𝐾
𝑚𝑜𝑙 ∗ 𝐾
𝑱
𝑾𝟑𝟒 = 𝟏𝟕𝟔 Answer
𝒎𝒐𝒍

 We know that,

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∆𝑈34 = 𝐶𝑉 ∆𝑇
5
∆𝑈34 = 𝑅(𝑇4 − 𝑇3 )
2
5 𝐽
∆𝑈34 = ∗ 8.314 ∗ (378.83 − 400)𝐾
2 𝑚𝑜𝑙 ∗ 𝐾
𝑱
∆𝑼𝟑𝟒 = −𝟒𝟒𝟎 Answer
𝒎𝒐𝒍

Step 41, an adiabatic process,


 Since
 For an adiabatic process there is no exchange of heat
 Therefore,
𝑸𝟒𝟏 = 𝟎
 We know that,

∆𝑈41 = 𝐶𝑉 ∆𝑇
5
∆𝑈41 = 𝑅(𝑇1 − 𝑇4 )
2
5 𝐽
∆𝑈41 = ∗ 8.314 ∗ (600 − 378.83) 𝐾
2 𝑚𝑜𝑙 ∗ 𝐾
𝐽
∆𝑈41 = 4597
𝑚𝑜𝑙
𝑱
∆𝑼𝟒𝟏 = 𝟒. 𝟓𝟗𝟕 ∗ 𝟏𝟎𝟑 Answer
𝒎𝒐𝒍

 We know that

∆𝐻41 = 𝐶𝑃 ∆𝑇
7
∆𝐻41 = 𝑅(𝑇1 − 𝑇4 )
2
7 𝐽
∆𝐻41 = ∗ 8.314 ∗ (600 − 378.83) 𝐾
2 𝑚𝑜𝑙 ∗ 𝐾
𝐽
∆𝐻41 = 6435.8
𝑚𝑜𝑙
𝟑 𝑱
∆𝑯𝟒𝟏 = 𝟔. 𝟒𝟑𝟓𝟖 ∗ 𝟏𝟎 Answer
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈41 = 𝑄41 + 𝑊41


∆𝑈41 = 𝑊41
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2013

𝑱
𝑾𝟒𝟏 = 𝟒. 𝟓𝟗𝟕 ∗ 𝟏𝟎𝟑 Answer
𝒎𝒐𝒍

Problem 3.10:

An ideal gas, CP= (5/2) R and CV= (3/2) R is changed from P1 = 1bar and 𝑽𝒕𝟏 = 12m3 to
P2 = 12 bar and 𝑽𝒕𝟐 = 1 m3 by the following mechanically reversible processes:
a) Isothermal compression
b) Adiabatic compression followed by cooling at constant pressure.
c) Adiabatic compression followed by cooling at constant volume.
d) Heating at constant volume followed by cooling at constant pressure.
e) Cooling at constant pressure followed by heating at constant volume.
Calculate Q, W, change in U, and change in H for each of these processes, and sketch
the paths of all processes on a single PV diagram.

Given Data:

5
𝐶𝑃 = 𝑅
2
3
𝐶𝑉 = 𝑅
2
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃1 = 1 𝑏𝑎𝑟
𝑉1𝑡 = 12 𝑚3
𝐹𝑖𝑛𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃2 = 12 𝑏𝑎𝑟
𝑉2𝑡 = 1 𝑚3
𝑄 =?
𝑊 =?
∆𝐻 =?
∆𝑈 =?

Solution:
 Since
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
 Therefore, for all parts of the problem,

∆𝑯 = 𝟎
∆𝑼 = 𝟎

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(a)

Isothermal compression,
 For an isothermal process, we have
𝑃2
𝑄 = −𝑅𝑇1 ln
𝑃1
 Since
 For an ideal gas, we have
𝑃1 V1 = 𝑅𝑇1
 Therefore,
𝑃2
𝑄 = −𝑃1 V1 ln
𝑃1
12 101325 N J 1𝐤𝐉
𝑄 = −1 𝑏𝑎𝑟 ∗ 12 𝑚3 ∗ ln ∗ ∗ ∗
1 1.01325 bar ∗ m2 Nm 1000 J
𝑸 = −𝟐𝟗𝟖𝟏. 𝟖𝟖 𝒌𝑱 Answer
 According to first law of thermodynamics

∆𝑈 = 𝑄 + 𝑊
0=𝑄+𝑊
𝑊 = −𝑄
𝑾𝟏𝟐 = 𝟐𝟗𝟖𝟏. 𝟖𝟖 𝒌𝑱 Answer

(b)

Adiabatic compression followed by cooling at constant pressure


 Since
 For an adiabatic process, there is no exchange of heat
 Therefore,

𝑸=𝟎 Answer

 The process completes in two steps


 First step, an adiabatic compression to final pressure P2 , intermediate volume can be given as

𝑃2 (𝑉 ′ )𝛾 = 𝑃1 𝑉1
1
𝑃1 𝛾
𝑉 ′ = 𝑉1 ( )
𝑃2

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 For mono atomic gas, we have

𝛾 = 1.67
1
1 1.67
𝑉 ′ = 12𝑚3 ∗ ( )
12
′ 𝟑
𝑽 = 𝟐. 𝟕𝟏 𝒎
 We know that,

𝑃2 𝑉 ′ − 𝑃1 𝑉1
𝑊1 =
𝛾−1
(12∗2.71−1∗12)𝑏𝑎𝑟∗𝑚3 101325 N J 1𝐤𝐉
𝑊1 = ∗ ∗ ∗
1.67−1 1.01325 bar∗m2 Nm 1000 J
𝑾𝟏 = 𝟑𝟎𝟔𝟑 𝒌𝑱 → (𝟏)
 Second step, cooling at constant pressure P2
 We know that, for a mechanically reversible process

𝑊2 = −𝑃2 (𝑉2 − 𝑉 ′ )
101325 𝑁 𝐽 1𝒌𝑱
𝑊2 = −12 𝑏𝑎𝑟 (1 − 2.71)𝑚3 ∗ ∗ ∗
1.01325 𝑏𝑎𝑟 ∗ 𝑚2 𝑁𝑚 1000 𝐽
𝑾𝟐 = 𝟐𝟎𝟓𝟐 𝒌𝑱 → (𝟐)
 Now
𝑊 = 𝑊1 + 𝑊2
𝑊 = (3063 + 2052)𝑘𝐽
𝑾 = 𝟓𝟏𝟏𝟓 𝒌𝑱 Answer

(c)

Adiabatic compression followed by cooling at constant volume


 Since
 For an adiabatic process, there is no exchange of heat
 Therefore,

𝑸=𝟎 Answer

 First step, an adiabatic compression to volume V2 , intermediate pressure can be given as


𝑃′ 𝑉2 𝛾 = 𝑃1 𝑉1
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𝑉1 𝛾
𝑃 = 𝑃1 ( )
𝑉2
 For mono atomic gas, we have

𝛾 = 1.67


12 1.67
𝑃 = 1 𝑏𝑎𝑟 ( )
1

𝑷 = 𝟔𝟑. 𝟒𝟐 𝒃𝒂𝒓
 We know that,

𝑃′ 𝑉2 −𝑃1 𝑉1
𝑊1 =
𝛾−1
(63.42 ∗ 1 − 1 ∗ 12)𝑏𝑎𝑟 ∗ 𝑚3 101325 𝑁 𝐽 1𝒌𝑱
𝑊1 = ∗ ∗ ∗
1.67 − 1 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 𝑁𝑚 1000 𝐽
𝑾𝟏 = 𝟕𝟔𝟕𝟒. 𝟕𝟔 𝒌𝑱
 Second step, cooling at constant Volume,
 Therefore, No work will be done

𝑾𝟐 = 𝟎
 Now
𝑊 = 𝑊1 + 𝑊2
𝑊 = (7674.76 + 0)𝑘𝐽
𝑾 = 𝟕𝟔𝟕𝟒. 𝟕𝟔 𝒌𝑱 Answer

(d)

Heating at constant volume followed by cooling at constant pressure


 The process completes in two steps
 Step 1, Heating at constant volume to P2
 Therefore no work will be done
𝑾𝟏 = 𝟎
 Step 2, Cooling at constant pressure P2 To V2
 We know that, for a mechanically reversible process

𝑊2 = −𝑃2 ∆𝑉
𝑊2 = −𝑃2 (𝑉2 − 𝑉1 )
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101325 𝑁 𝐽 1𝒌𝑱
𝑊2 = −12 𝑏𝑎𝑟(1 − 12)𝑚3 ∗ ∗ ∗
1.01325 𝑏𝑎𝑟 ∗ 𝑚2 𝑁𝑚 1000 𝐽
𝑾𝟐 = 𝟏𝟑𝟐𝟎𝟎 𝒌𝑱
 Now
𝑊 = 𝑊1 + 𝑊2
𝑊 = (0 + 13200)𝑘𝐽
𝑾 = 𝟏𝟑𝟐𝟎𝟎 𝒌𝑱 Answer
 According to first law of thermodynamics

∆𝑈 = 𝑄 + 𝑊
0=𝑄+𝑊
𝑄 = −𝑊
𝑸 = −𝟏𝟑𝟐𝟎𝟎 𝒌𝑱 Answer

(e)

Cooling at constant pressure followed by heating at constant volume


 The process completes in two steps
 Step 1, Cooling at constant Pressure P1 to V2
 Therefore, for a mechanically reversible process

𝑊1 = −𝑃1 ∆𝑉
𝑊1 = −𝑃1 (𝑉2 − 𝑉1 )
101325 𝑁 𝐽 1𝒌𝑱
𝑊1 = −1 𝑏𝑎𝑟(1 − 12)𝑚3 ∗ ∗ ∗
1.01325 𝑏𝑎𝑟 ∗ 𝑚2 𝑁𝑚 1000 𝐽
𝑾𝟏 = 𝟏𝟏𝟎𝟎 𝒌𝑱
 Step 1, Heating at constant Volume V2 to pressure P2
 Therefore no work will be done
𝑾𝟐 = 𝟎
 Now
𝑊 = 𝑊1 + 𝑊2
𝑊 = (1100 + 0)𝑘𝐽
𝑾 = 𝟏𝟏𝟎𝟎 𝒌𝑱 Answer
 According to first law of thermodynamics

∆𝑈 = 𝑄 + 𝑊
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0=𝑄+𝑊
𝑄 = −𝑊
𝑸 = −𝟏𝟏𝟎𝟎 𝒌𝑱 Answer

Problem 3.11:
𝒅𝑻
The environmental lapse rate characterizes the local variation of temperature with
𝒅𝒛
elevation in the earth's atmosphere. Atmospheric pressure varies with elevation
according to the hydrostatic formula,
𝒅𝑷
= −𝓜𝝆𝒈
𝒅𝒛

Where M is a molar mass, ρ is molar density and g is the local acceleration of gravity.
Assume that the atmosphere is an ideal gas, with T related to P by the polytropic formula
equation (3.35 c). Develop an expression for the environmental lapse rate in relation to
M, g, R, and δ.

Solution:
 Given that

𝑑𝑃
= −ℳ𝜌𝑔 → (1)
𝑑𝑧
 The polytropic relation is

1−𝛿
𝑇𝑃 𝛿 = 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡
 Or

1−𝛿 1−𝛿
𝑇𝑃 𝛿 = 𝑇𝑜 𝑃𝑜 𝛿
 Where
 To =Temperature at sea level, so it is constant
 Po = Pressure at sea level, so it is constant

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𝑇 𝑇𝑜
𝛿−1
= δ−1
𝑃 𝛿
Po δ
𝛿−1
𝑇 𝑃 𝛿
=( )
𝑇𝑜 𝑃𝑜
𝛿
𝑇 𝛿−1 𝑃
( ) =
𝑇𝑜 𝑃𝑜
𝛿
𝑇 𝛿−1
𝑃 = 𝑃𝑜 ( ) → (𝑎)
𝑇𝑜
𝑃𝑜 𝛿
𝑃= 𝛿
∗ 𝑇 𝛿−1

𝑇𝑜 𝛿−1

 Differentiate w.r.t to Temperature on both sides

𝑑𝑃 𝑃𝑜 𝛿 1
= 𝛿
∗ ∗𝑇 𝛿−1
𝑑𝑇 𝛿−1
𝑇𝑜 𝛿−1
𝑃𝑜 𝛿 1
𝑑𝑃 = 𝛿
∗ ∗ 𝑇 𝛿−1 𝑑𝑇 → (2)
𝛿−1
𝑇𝑜 𝛿−1
 We know that, for an ideal gas

𝑃
𝜌=
𝑅𝑇
 Where
 R = Specific gas constant = R′ /ℳ
 Put (a) in above equation

𝛿
1 𝑇 𝛿−1
𝜌= ∗ 𝑃𝑜 ( )
𝑅𝑇 𝑇𝑜
 Put in (1)

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𝛿
𝑑𝑃 1 𝑇 𝛿−1
= −ℳ𝑔 ∗ 𝑃𝑜 ( )
𝑑𝑧 𝑅𝑇 𝑇𝑜
𝛿
1 𝑇 𝛿−1
𝑑𝑃 = −ℳ𝑔 ∗ 𝑃𝑜 ( ) ∗ 𝑑𝑧
𝑅𝑇 𝑇𝑜
 Put (2) in above

𝛿
1
𝑃𝑜 𝛿 1 𝑇 𝛿−1
𝛿 ∗ ∗𝑇 𝛿−1 𝑑𝑇 = −ℳ𝑔 ∗ 𝑃𝑜 ( ) ∗ 𝑑𝑧
𝛿−1 𝑅𝑇 𝑇𝑜
𝑇𝑜 𝛿−1
𝛿 𝛿
𝑑𝑇 𝛿 − 1 ℳ𝑔 𝑃𝑜 𝑇𝑜 𝛿−1 𝑇 𝛿−1
=− ∗ ∗ ∗ 𝛿
∗ 1
𝑑𝑧 𝛿 𝑅 𝑃𝑜
𝑇𝑜 𝛿−1 𝑇 ∗ 𝑇 𝛿−1
𝛿 𝛿
𝑑𝑇 𝛿 − 1 ℳ𝑔 𝑃𝑜 𝑇𝑜 𝛿−1 𝑇 𝛿−1
=− ∗ ∗ ∗ 𝛿
∗ 𝛿
𝑑𝑧 𝛿 𝑅 𝑃𝑜
𝑇𝑜 𝛿−1 𝑇 𝛿−1
𝒅𝑻 𝜹 𝓜𝒈
=− ∗ Proved
𝒅𝒛 𝜹−𝟏 𝑹

Problem 3.12:

An evacuated tank is filled with gas from a constant pressure line. Develop an expression
relating the temperature of the gas in the tank to temperature T’ of the gas in line.
Assume that gas is ideal with constant heat capacities, and ignore heat transfer between
the gas and the tank. Mass and energy balances for this problem are treated in Ex. 2.13.

Solution:
 Choose the tank as the control volume. There is no work, no heat transfer & kinetic & potential
energy changes are assumed negligible.
 Therefore, applying energy balance

𝑑(𝑚𝑈)𝑡𝑎𝑛𝑘
+ ∆(𝐻𝑚) = 0
𝑑𝑡
𝑑(𝑚𝑈)𝑡𝑎𝑛𝑘
+ 𝐻′′ 𝑚′′ − 𝐻′ 𝑚′ = 0
𝑑𝑡
 Since
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 Tank is filled with gas from an entrance line, but no gas is being escaped out,
 Therefore,

𝑑(𝑚𝑈)𝑡𝑎𝑛𝑘
+ 0 − 𝐻 ′ 𝑚′ = 0
𝑑𝑡
𝑑(𝑚𝑈)𝑡𝑎𝑛𝑘
− 𝐻′ 𝑚′ = 0 → (1)
𝑑𝑡
 Where prime (‘) denotes the entrance stream
 Applying mass balance

𝑑𝑚𝑡𝑎𝑛𝑘
𝑚′ = → (2)
𝑑𝑡
 Combining equation (1) & (2)

𝑑(𝑚𝑈)𝑡𝑎𝑛𝑘 𝑑𝑚𝑡𝑎𝑛𝑘
− 𝐻′ =0
𝑑𝑡 𝑑𝑡
1
{𝑑(𝑚𝑈)𝑡𝑎𝑛𝑘 − 𝐻′ 𝑑𝑚𝑡𝑎𝑛𝑘 } = 0
𝑑𝑡
𝑑(𝑚𝑈)𝑡𝑎𝑛𝑘 = 𝐻′ 𝑑𝑚𝑡𝑎𝑛𝑘
 Integrating on both sides
𝑚2 𝑚2

∫ 𝑑(𝑚𝑈)𝑡𝑎𝑛𝑘 = 𝐻 ∫ 𝑑𝑚𝑡𝑎𝑛𝑘
𝑚1 𝑚1
∆(𝑚𝑈)𝑡𝑎𝑛𝑘 = 𝐻′ (𝑚2 − 𝑚1 )

𝑚2 𝑈2 − 𝑚1 𝑈1 = 𝐻′ (𝑚2 − 𝑚1 )
 Because mass in the tank initially is zero, therefore

𝑚1 = 0

𝑚2 𝑈2 = 𝐻′ 𝑚2

𝑈2 = 𝐻′ → (3)
 We know that
𝑈 = 𝐶𝑉 𝑇
𝑈2 = 𝐶𝑉 𝑇2 → (𝑎)
 Also

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𝐻′ = 𝐶𝑃 𝑇 ′ → (𝑏)
 Put (a) & (b) in (3)

𝐶𝑉 𝑇 = 𝐶𝑃 𝑇 ′
𝐶𝑃 ′
𝑇= 𝑇
𝐶𝑉
 Since heat capacities are constant, therefore

𝐶𝑃
𝛾=
𝐶𝑉
𝑻 = 𝜸𝑻′ Proved

Problem 3.14:

A tank of 0.1-m3 volume contains air at 25 oC and 101.33 kPa. The tank is connected to
a compressed-air line which supplies air at the constant conditions of 45oC and 1,500
kPa. A valve in the line is cracked so that air flows slowly into the tank until the pressure
equals the line pressure. If the process occurs slowly enough that the temperature in the
tank remains at 25 oC, how much heat is lost from the tank? Assume air to be an ideal
gas for which CP = (7/2) R and CV = (5/2) R

Given Data:

𝑉𝑜𝑙𝑢𝑚𝑒 = 𝑉 = 0.1 𝑚3
𝑇1 = 25 𝑜.𝐶 = 298 K
𝑃1 = 101.33 𝑘𝑃𝑎
𝑇2 = 45 𝑜.𝐶 = 318 𝐾
𝑃2 = 1500 𝑘𝑃𝑎
𝐻𝑒𝑎𝑡 𝑙𝑜𝑠𝑡 = 𝑄 =?
7
𝐶𝑃 = 𝑅
2
5
𝐶𝑉 = 𝑅
2

Solution:
 According to first law of thermodynamics

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∆𝑈 = 𝑄 + 𝑊 → (1)
 Since

∆𝐻 = ∆𝑈 + ∆(𝑃𝑉)
∆𝑈 = ∆𝐻 − ∆(𝑃𝑉)
∆𝑈 = ∆𝐻 − 𝑃∆𝑉 − 𝑉∆𝑃 → (𝑎)
 Also, we know that

𝑊 = −𝑃∆𝑉 → (𝑏)
 Put (a) & (b) in (1)

∆𝐻 − 𝑃∆𝑉 − 𝑉∆𝑃 = 𝑄 − 𝑃∆𝑉


∆𝐻 − 𝑉∆𝑃 = 𝑄 → (2)
 Also, we have

∆𝐻 = 𝑛𝐶𝑃 ∆𝑇
∆𝐻 = 𝑛𝐶𝑃 (𝑇2 − 𝑇1 )
 Put in (2)

𝑛𝐶𝑃 (𝑇2 − 𝑇1 ) − 𝑉∆𝑃 = 𝑄 → (3)


 For “n”

 We know that for an ideal gas,

𝑃𝑉 = 𝑛𝑅𝑇
 Initial number of moles of gas can be obtained as,

𝑃1 𝑉 = 𝑛1 𝑅𝑇1
𝑃1 𝑉
𝑛1 =
𝑅𝑇1
 The final number of moles of gas at temperature T1 are

𝑃2 𝑉 = 𝑛2 𝑅𝑇1
𝑃2 𝑉
𝑛2 =
𝑅𝑇1

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 Now, Applying molar balance


𝑛 = 𝑛1 − 𝑛2
𝑃1 𝑉 𝑃2 𝑉
𝑛= −
𝑅𝑇1 𝑅𝑇1
(𝑃1 − 𝑃2 )𝑉
𝑛=
𝑅𝑇1
 Put in (3)

(𝑃1 − 𝑃2 )𝑉
𝐶𝑃 (𝑇2 − 𝑇1 ) − 𝑉∆𝑃 = 𝑄
𝑅𝑇1
(𝑃1 − 𝑃2 )𝑉 7
∗ 𝑅 ∗ (𝑇2 − 𝑇1 ) − 𝑉∆𝑃 = 𝑄
𝑅𝑇1 2
(𝑃1 − 𝑃2 )𝑉 7
∗ ∗ (𝑇2 − 𝑇1 ) − 𝑉(𝑃2 − 𝑃1 ) = 𝑄
𝑇1 2

(101.33 − 1500)𝑘𝑃𝑎 ∗ 0.1𝑚3 7


∗ ∗ (318 − 298)𝐾
298 𝐾 2
3 (1500
− 0.1 𝑚 − 101.33)𝑘𝑃𝑎 = 𝑄
1 𝑘𝑁 1𝒌𝑱
𝑄 = −172.717 𝑚3 𝑘𝑃𝑎 ∗ ∗
1 𝑘𝑃𝑎 ∗ 𝑚2 1 𝑘𝑁𝑚
𝑸 = −𝟏𝟕𝟐. 𝟕𝟏𝟕𝒌𝑱 Answer

Problem 3.17:

A rigid, no conducting tank with a volume of 4 m3 is divided into two unequal parts by a
thin membrane. One side of the membrane, representing 1/3 of the tank, contains
nitrogen gas at 6 bars and 100 oC, and the other side, representing 2/3 of the tank, is
evacuated. The membrane ruptures and the gas fills the tank.
a) What is the final, temperature of the gas? How much work is done? Is the
process reversible?
b) Describe a reversible process by which the gas can be returned to its initial state,
How much work is done

Assume nitrogen is an ideal gas for which CP = (7/2) R & CV = (5/2) R

Given Data:

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𝑉𝑜𝑙𝑢𝑚𝑒 𝑜𝑓 𝑡ℎ𝑒 𝑡𝑎𝑛𝑘 = 𝑉1 = 4 𝑚3


1 4
𝑉2 = 𝑉1 ∗ = 𝑚3
3 3
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃2 = 6 𝑏𝑎𝑟
𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇1 = 100 o.C
2 8
𝑉3 = 𝑉1 ∗ = 𝑚3
3 3
Solution:
(a)

𝐹𝑖𝑛𝑎𝑙 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇2 =?
 According to first law of thermodynamics

∆𝑈 = 𝑄 + 𝑊
 Since
 No work is done & no heat is transferred
 Therefore

𝑄=𝑊=0

∆𝑈 = 0
𝑚𝐶𝑉 ∆𝑇 = 0
∆𝑇 = 0
𝑇2 − 𝑇1 = 0
𝑇2 = 𝑇1
𝑻𝟐 = 𝟏𝟎𝟎 ℃ Answer
 No, process is not reversible

(b)

 Since

 Therefore, the process is isothermal


 For an isothermal process we have

𝑉2
𝑊 = −𝑅𝑇2 ln
𝑉1
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 As, for an ideal gas

𝑃2 𝑉2 = 𝑅𝑇2
𝑉2
𝑊 = −𝑃2 𝑉2 ln
𝑉1
4 4
𝑊 = −6 𝑏𝑎𝑟 ∗ 𝑚3 ln
3 3∗4
101325𝑁 𝑘𝐽
𝑊 = 8.788 𝑏𝑎𝑟 ∗ 𝑚3 ∗ ∗ 1
1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1000𝑁𝑚
𝑾 = 𝟖𝟕𝟖. 𝟖 𝒌𝑱 Answer

Problem 3.18:

An ideal gas initially at 30 0C and 100 kPa undergoes the following cyclic processes in a
closed system:
a) In mechanically reversible processes, it is first compressed adiabatically to 500
kPa then cooled at a constant pressure of 500 kPa to 30 0C and finally expanded
isothermally to its original state
b) The cycle traverses exactly the same changes of state but each step is irreversible
with an efficiency of 80% compared with the corresponding mechanically
reversible process NOTE: the initial step can no longer be adiabatic
Find Q W ∆U and ∆H for each step of the process and for the cycle Take Cp = (7/2) R
and CV = (5/2) R

Given Data:

𝑇1 = 30 0.𝐶
𝑇1 = 303.15 K
𝑃1 = 100 𝑘𝑃𝑎
𝑄 =?
𝑊 =?
∆𝑈 =?
∆𝐻 =?
7
𝐶𝑃 = R
2
5
CV = R
2
Solution:

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(a)

𝑃2 = 500 𝑘𝑃𝑎
1) Adiabatic Compression from point 1 to point 2
𝑄12 = 0
 Now, from first law of thermodynamics,

∆𝑈12 = 𝑄12 + 𝑊12


∆𝑈12 = 𝑊12

𝑊12 = ∆𝑈12 = 𝐶𝑉 ∆𝑇12


5
𝑊12 = ∆𝑈12 = 𝑅(𝑇2 − 𝑇1 ) → (1)
2
 For ‘T2’
 We know that

𝛾−1
𝑇2 𝑃2 𝛾
=( )
𝑇1 𝑃1
𝛾−1
𝑃2 𝛾
𝑇2 = 𝑇1 ( )
𝑃1
1.4−1
500 1.4
𝑇2 = 303.15 𝐾 ( )
100
𝑻𝟐 = 𝟒𝟖𝟎. 𝟏𝟑 𝑲
 Put in (1)

5 𝐽 𝑘𝐽
𝑊12 = ∆𝑈12 = ∗ 8.314 (480.13 − 303.15)𝐾 ∗ 1
2 𝑚𝑜𝑙∗𝐾 1000𝐽
𝒌𝑱
𝑾𝟏𝟐 = ∆𝑼𝟏𝟐 = 𝟑. 𝟔𝟕𝟗
𝒎𝒐𝒍

 Also, we have
∆𝐻12 = 𝐶𝑃 (𝑇2 − 𝑇1 )
7 𝐽 𝑘𝐽
∆𝐻12 = ∗ 8.314 (480.13 − 303.15)𝐾 ∗ 1
2 𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽
𝒌𝑱
∆𝑯𝟏𝟐 = 𝟓. 𝟏𝟓
𝒎𝒐𝒍
2) Cooling at constant pressure from point 2 to point 3
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 Therefore at constant pressure we have,

𝑄23 = ∆𝐻23 = 𝐶𝑃 ∆𝑇23


7
𝑄23 = ∆𝐻23 = 𝑅(𝑇3 − 𝑇2 )
2
 Here

𝑇3 = 303.15 K

7 𝐽 𝑘𝐽
𝑄23 = ∆𝐻23 = ∗ 8.314 (303.15 − 480.13)𝐾 ∗ 1
2 𝑚𝑜𝑙∗𝐾 1000 𝐽
𝒌𝑱
𝑸𝟐𝟑 = ∆𝑯𝟐𝟑 = −𝟓. 𝟏𝟓
𝒎𝒐𝒍

 Also, we have
∆𝑈23 = 𝐶𝑉 (𝑇3 − 𝑇2 )
5 𝐽 𝑘𝐽
∆𝑈23 = ∗ 8.314 (303.15 − 480.13)𝐾 ∗ 1
2 𝑚𝑜𝑙∗𝐾 1000 𝐽
𝒌𝑱
∆𝑼𝟐𝟑 = −𝟑. 𝟔𝟕𝟗
𝒎𝒐𝒍
 Now, from first law of thermodynamics,

∆𝑈23 = 𝑄23 + 𝑊23


𝑊23 = ∆𝑈23 − 𝑄23
𝑊23 = −3.679 + 5.15
𝒌𝑱
𝑾𝟐𝟑 = 𝟏. 𝟒𝟕𝟏
𝒎𝒐𝒍

3) Isothermal expansion from point 3 to point 1


 Since for an isothermal process temperature remains constant
 Therefore,

∆𝑈31 = ∆𝐻31 = 0
 Here

𝑃3 = 𝑃2 = 500 𝑘𝑃𝑎
 For an Isothermal process we have

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𝑃3
𝑊31 = −𝑅𝑇3 𝑙𝑛
𝑃1
𝐽 500 1 𝑘𝐽
𝑊31 = −8.314 ∗ 303.15 𝐾 ∗ ln ∗
𝑚𝑜𝑙∗𝐾 100 1000 𝐽
𝒌𝑱
𝑾𝟑𝟏 = −𝟒. 𝟎𝟓𝟔
𝒎𝒐𝒍
 According to first law of thermodynamics

∆𝑈31 = 𝑄31 + 𝑊31

0 = 𝑄31 + 𝑊31
𝑄31 = −𝑊31
𝒌𝑱
𝑸𝟑𝟏 = 𝟒. 𝟎𝟓𝟔
𝒎𝒐𝒍

 For the complete cycle,

𝑄 = 𝑄12 + 𝑄23 + 𝑄31


𝑄 = 0 − 5.15 + 4.056
𝒌𝑱
𝑸 = −𝟏. 𝟎𝟗𝟒 Answer
𝒎𝒐𝒍

𝑊 = 𝑊12 + 𝑊23 + 𝑊31


𝑊 = 3.679 + 1.471 − 4.056
𝒌𝑱
𝑾 = 𝟏. 𝟎𝟗𝟒 Answer
𝒎𝒐𝒍
∆𝐻 = ∆𝐻12 + ∆𝐻23 + ∆𝐻31
∆𝐻 = 5.15 − 5.15 + 0
𝒌𝑱
∆𝑯 = 𝟎 Answer
𝒎𝒐𝒍
∆𝑈 = ∆𝑈12 + ∆𝑈23 + ∆𝑈31
∆𝑈 = 3.679 − 3.679 + 0
𝒌𝑱
∆𝑼 = 𝟎 Answer
𝒎𝒐𝒍

(b)

 If each step that is 80% accomplishes the same change of state then values of ∆𝑈 & ∆𝐻 will remain
same as in part (a) but values of Q & W will change.
1. Adiabatic Compression from point 1 to point 2

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𝑊12
𝑊12 =
0.8
3.679
𝑊12 =
0.8
𝒌𝑱
𝑾𝟏𝟐 = 𝟒. 𝟓𝟗𝟖
𝒎𝒐𝒍

 According to first law of thermodynamics


∆𝑈12 = 𝑄12 + 𝑊12
𝑘𝐽 𝑘𝐽
3.679 = 𝑄12 + 4.598
𝑚𝑜𝑙 𝑚𝑜𝑙
𝑘𝐽 𝑘𝐽
𝑄12 = 3.679 − 4.598
𝑚𝑜𝑙 𝑚𝑜𝑙
𝒌𝑱
𝑸𝟏𝟐 = −𝟎. 𝟗𝟐
𝒎𝒐𝒍
2. Cooling at constant pressure from point 2 to point 3

𝑊23
𝑊23 =
0.8
1.471
𝑊23 =
0.8
𝒌𝑱
𝑾𝟐𝟑 = 𝟏. 𝟖𝟑𝟗
𝒎𝒐𝒍
 According to first law of thermodynamics

∆𝑈23 = 𝑄23 + 𝑊23


𝑘𝐽 𝑘𝐽
−3.679 = 𝑄23 + 1.839
𝑚𝑜𝑙 𝑚𝑜𝑙
𝑘𝐽 𝑘𝐽
𝑄23 = −3.679 − 1.839
𝑚𝑜𝑙 𝑚𝑜𝑙
𝒌𝑱
𝑸𝟐𝟑 = −𝟓. 𝟓𝟏𝟖
𝒎𝒐𝒍
3. Isothermal expansion from point 3 to point 1
 Since initial step can no longer be adiabatic , therefore

𝑊31 = 𝑊31 ∗ 0.8

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𝑘𝐽
𝑊31 = −4.056 ∗ 0.8
𝑚𝑜𝑙
𝒌𝑱
𝑾𝟑𝟏 = 𝟑. 𝟐𝟒𝟓
𝒎𝒐𝒍
 According to first law of thermodynamics

∆𝑈31 = 𝑄31 + 𝑊31


𝑄31 = −𝑊31 + 0
𝒌𝑱
𝑸𝟑𝟏 = 𝟑. 𝟐𝟒𝟓
𝒎𝒐𝒍
 For the complete cycle,

𝑄 = 𝑄12 + 𝑄23 + 𝑄31


𝑄 = −0.92 − 5.518 + 3.245
𝒌𝑱
𝑸 = −𝟑. 𝟏𝟗𝟑 Answer
𝒎𝒐𝒍

𝑊 = 𝑊12 + 𝑊23 + 𝑊31


𝑊 = 4.598 + 1.839 − 3.245
𝒌𝑱
𝑾 = 𝟑. 𝟏𝟗𝟐 Answer
𝒎𝒐𝒍

Problem 3.19:

One cubic meter of an ideal gas at 600 K and 1,000 kPa expands to five times its initial
volume as follows:
a) By a mechanically reversible, isothermal process
b) By a mechanically reversible adiabatic process
c) By adiabatic irreversible process in which expansion is against a restraining
pressure of 100 kPa
For each case calculate the final temperature, pressure and the work done by the gas,
Cp=21 J mol-1K-1.

Given Data:

𝑉1 = 1 𝑚3
𝑇1 = 600 𝐾
𝑃1 = 1000 𝑘𝑃𝑎
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𝑉2 = 5𝑉1
𝑉2 = 5 𝑚3
𝐽
𝐶𝑃 = 21
𝑚𝑜𝑙 𝐾
𝐶𝑉 =?
𝑇2 =?
𝑃2 =?
𝑊 =?

Solution:
 We know that,
𝐶𝑃 − 𝐶𝑉 = 𝑅
𝐶𝑉 = 𝐶𝑃 − 𝑅
𝐽
𝐶𝑉 = (21 − 8.314)
𝑚𝑜𝑙 ∗ 𝐾
𝐽
𝐶𝑉 = 12.686
𝑚𝑜𝑙 ∗ 𝐾
 As

𝐶𝑃
𝛾=
𝐶𝑉
𝜸 = 𝟏. 𝟔𝟓𝟓𝟒
(a)

 Since, for an isothermal process


 Temperature remains constant, therefore

𝑻𝟐 = 𝑻𝟏 = 𝟔𝟎𝟎 𝑲 Answer

 For an ideal gas we have

𝑃1 𝑉1 𝑃2 𝑉2
=
𝑇1 𝑇2
𝑃1 𝑉1 𝑇2
𝑃2 = ∗
𝑇1 𝑉2
1000 𝑘𝑃𝑎 ∗ 1 𝑚3 600 𝐾
𝑃2 = ∗
600 𝐾 5 𝑚3
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𝑷𝟐 = 𝟐𝟎𝟎 𝒌𝑷𝒂 Answer

 We know that, for an isothermal process

𝑉2
𝑊 = −𝑅𝑇1 ln
𝑉1
 Since

𝑃1 𝑉1 = 𝑅𝑇1
 Therefore,

𝑉2
𝑊 = −𝑃1 𝑉1 ln
𝑉1
5 𝑁 𝐽
𝑊 = −1000 𝑘𝑃𝑎 ∗ 1 𝑚3 ln ∗ ∗
1 𝑃𝑎 ∗ 𝑚2 𝑁𝑚
𝑾 = −𝟏𝟔𝟎𝟗. 𝟒𝟑 𝒌𝑱 Answer
(b)

 We know that, for an adiabatic process

𝑃1 𝑉1 𝛾 = 𝑃2 𝑉2 𝛾
𝑉1 𝛾
𝑃2 = 𝑃1 ( )
𝑉2
1 1.6554
𝑃2 = 1000 𝑘𝑃𝑎 ∗ ( )
5
𝑷𝟐 = 𝟔𝟗. 𝟔𝟓 𝒌𝑷𝒂 Answer

 For an ideal gas we have


𝑃1 𝑉1 𝑃2 𝑉2
=
𝑇1 𝑇2
𝑃2 𝑉2
𝑇2 = ∗𝑇
𝑃1 𝑉1 1
69.65 kPa ∗ 5 m3
𝑇2 = ∗ 600 K
1000 kPa ∗ 1 m3
𝑻𝟐 = 𝟐𝟎𝟖. 𝟗𝟓 𝐊 Answer
 For an adiabatic process work done is

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𝑃2 𝑉2 −𝑃1 𝑉1
𝑊=
𝛾−1
(69.65 ∗ 5 − 1000 ∗ 1 ) 𝑘𝑃𝑎 ∗ 𝑚3 𝑁 𝐽
𝑊= ∗
1.6554 − 1 𝑃𝑎 ∗ 𝑚2 𝑁𝑚
𝑾 = −𝟗𝟗𝟒. 𝟒𝟑 𝒌𝑱 Answer

(c)

𝑃𝑟 = 100 𝑘𝑃𝑎
 Since, for an adiabatic process

𝑄=0
 According to first law of thermodynamics

∆𝑈 = 𝑄 + 𝑊
∆𝑈 = 𝑊
∆𝑈 = 𝑊 = −𝑃𝑟 𝑑𝑉
∆𝑈 = 𝑊 = −𝑃𝑟 (𝑉2 − 𝑉1 )
𝑁 𝐽
∆𝑈 = 𝑊 = −100(5 − 1)𝑘𝑃𝑎 ∗ 𝑚3 ∗ ∗
𝑃𝑎 ∗ 𝑚2 𝑁𝑚
∆𝑼 = −𝟒𝟎𝟎 𝒌𝑱
𝑛𝐶𝑉 ∆𝑇 = −400 𝑘𝐽
𝑛𝐶𝑉 (𝑇2 − 𝑇1 ) = −400 𝑘𝐽
−400 𝑘𝐽
𝑇2 = + 𝑇1 → (1)
𝑛𝐶𝑉
 For an ideal gas we have,

𝑃1 𝑉1 = 𝑛𝑅𝑇1
𝑃1 𝑉1
𝑛=
𝑅𝑇1
1000 𝑘𝑃𝑎 ∗ 1𝑚3 ∗ 𝑚𝑜𝑙 ∗ 𝐾 𝑘𝑁 𝑘𝐽
𝑛= ∗ ∗
8.314 𝐽 ∗ 600 𝐾 𝑘𝑃𝑎 ∗ 𝑚2 𝑘𝑁𝑚
𝒏 = 𝟎. 𝟐𝟎𝟎𝟓 𝒎𝒐𝒍
 Put in (1)

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400 𝑘𝐽∗𝑚𝑜𝑙∗𝐾 1000 𝐽


𝑇2 = − ∗ + 600 𝐾
0.2005 𝑚𝑜𝑙∗12.686 𝐽 1 𝑘𝐽
𝑇2 = −157.26 𝐾 + 600 𝐾
𝑻𝟐 = 𝟒𝟒𝟐. 𝟕𝟒 𝑲 Answe𝑟

 For an ideal gas we have

𝑃1 𝑉1 𝑃2 𝑉2
=
𝑇1 𝑇2
𝑃1 𝑉1 𝑇2
𝑃2 = ∗
𝑇1 𝑉2
1000 𝑘𝑃𝑎 ∗ 1 𝑚3 442.74 𝐾
𝑃2 = ∗
600 𝐾 5 𝑚3
𝑷𝟐 = 𝟏𝟒𝟕. 𝟓𝟖 𝒌𝑷𝒂 Answe𝑟

Problem 3.20:

One mole of air, initially at 150 0C and 8 bars undergoes the following mechanically
reversible changes. It expands isothermally to a pressure such that when it is cooled at
constant volume to 50 0C its final pressure is 3 bars. Assuming air is an ideal gas for
which CP = (7/2) R and CV = (5/2) R, calculate W, Q,∆𝑼, and ∆𝑯

Given Data:

𝑀𝑜𝑙𝑒 𝑜𝑓 𝑎𝑖𝑟 = 𝑛 = 1 𝑚𝑜𝑙


𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇1 = 150 0.𝐶 = 423.15 𝐾
𝐼𝑛𝑖𝑡𝑖𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃1 = 8 𝑏𝑎𝑟
𝐹𝑖𝑛𝑎𝑙 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇3 = 50 0.𝐶 = 323.15 𝐾
𝐹𝑖𝑛𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃3 = 3 𝑏𝑎𝑟
7
𝐶𝑃 = 𝑅
2
5
𝐶𝑉 = 𝑅
2

Solution:
 Since process is reversible
 Two different steps are used in this case to reach final state of the air.

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Step 12:
 For step 12 temperatures is constant,

𝑇1 = 𝑇2
 Therefore

∆𝑼𝟏𝟐 = ∆𝑯𝟏𝟐 = 𝟎
 For an isothermal process we have
𝑉1
𝑊12 = 𝑅𝑇1 ln
𝑉2
 As
𝑉2 = 𝑉3
𝑉1
𝑊12 = 𝑅𝑇1 ln → (1)
𝑉3
 We know that

𝑃1 𝑉1 𝑃3 𝑉3
=
𝑇1 𝑇3
𝑉1 𝑃3 ∗ 𝑇1
=
𝑉3 𝑇3 ∗ 𝑃1
𝑃1 ∗ 𝑇3
𝑊12 = 𝑅𝑇1 ln
𝑇1 ∗ 𝑃3
8.314 𝐽 ∗ 423.15 𝐾 1 𝑘𝐽 3 ∗ 423.15
𝑊12 = ∗ ∗ 𝑙𝑛
𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽 8 ∗ 323.15
𝒌𝑱
𝑾𝟏𝟐 = −𝟐. 𝟓𝟎𝟐
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈12 = 𝑄12 + 𝑊12


0 = 𝑄12 + 𝑊12
𝑄12 = −𝑊12
𝒌𝑱
𝑸𝟏𝟐 = 𝟐. 𝟓𝟎𝟐
𝒎𝒐𝒍

Step 23:
 For step 23 volume is constant,
 Therefore,
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𝑊23 = 0
 According to first law of thermodynamics

∆𝑈23 = 𝑄23 + 𝑊23


∆𝑈23 = 𝑄23 + 0
𝑄23 = ∆𝑈23
𝑄23 = ∆𝑈23 = 𝐶𝑉 ∆𝑇
𝑄23 = ∆𝑈23 = 𝐶𝑉 (𝑇3 − 𝑇2 )
5
𝑄23 = ∆𝑈23 = 𝑅(323.15 − 423.15)𝐾
2
5 𝐽 1 𝑘𝐽
𝑄23 = ∆𝑈23 = ∗ 8.314 ∗ (−100) 𝐾
2 𝑚𝑜𝑙∗𝐾 1000 𝐽
𝒌𝑱
𝑸𝟐𝟑 = ∆𝑼𝟐𝟑 = −𝟐. 𝟎𝟕𝟖𝟓
𝒎𝒐𝒍

 W e know that
∆𝐻23 = 𝐶𝑃 ∆𝑇
∆𝐻23 = 𝐶𝑃 (𝑇3 − 𝑇2 )
7 𝐽 1 𝑘𝐽
∆𝐻23 = ∗ 8.314 ∗ (423.15 − 323.15) 𝐾
2 𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽
𝒌𝑱
∆𝑯𝟐𝟑 = 𝟐. 𝟗𝟏
𝒎𝒐𝒍
 For the complete cycle,

𝑊𝑜𝑟𝑘 = 𝑊 = 𝑊12 + 𝑊23


𝑘𝐽
𝑊 = (−2.502 + 0)
𝑚𝑜𝑙
𝒌𝑱
𝑾 = −𝟐. 𝟓𝟎𝟐 Answe𝑟
𝒎𝒐𝒍

𝑄 = 𝑄12 + 𝑄23
𝑘𝐽
𝑄 = (2.502 − 2.0785)
𝑚𝑜𝑙
𝒌𝑱
𝑸 = 𝟎. 𝟒𝟐𝟒 Answe𝑟
𝒎𝒐𝒍

∆𝑈 = ∆𝑈12 + ∆𝑈23
𝑘𝐽
∆𝑈 = (0 − 2.0785)
𝑚𝑜𝑙
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𝒌𝑱
∆𝑼 = −𝟐. 𝟎𝟕𝟖𝟓 Answe𝑟
𝒎𝒐𝒍

∆𝐻 = ∆𝐻12 + ∆𝐻23
𝑘𝐽
∆𝐻 = (0 − 2.91)
𝑚𝑜𝑙
𝒌𝑱
∆𝑯 = −𝟐. 𝟗𝟏 Answe𝑟
𝒎𝒐𝒍

Problem 3.21:

An ideal gas flows through a horizontal tube at steady state. No heat is added and no
shaft work is done. The cross-sectional area of the tube changes with length, and this
causes the velocity to change. Derive an equation relating the temperature to the velocity
of the gas. If nitrogen at 150 0C flows past one section of the tube with a velocity of 2.5
m/s, what is the temperature at another section where its velocity is 50 m/s? Let CP =
(7/2) R

Given Data:

𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇1 = 150 0.𝐶 = 423.15 K


𝑚
𝑉𝑒𝑙𝑜𝑐𝑖𝑡𝑦 = 𝑢1 = 2.5
𝑠𝑒𝑐
𝑇2 =?
𝑚
𝑢2 = 50
𝑠𝑒𝑐
7
𝐶𝑃 = 𝑅
2
𝑔
𝑀𝑜𝑙𝑒𝑐𝑢𝑎𝑙𝑟 𝑤𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 = 28
𝑚𝑜𝑙

Solution:
 Applying energy balance for steady state flow process

∆𝑢2
∆𝐻 + + 𝑔∆𝑧 = 𝑄 + 𝑊𝑆
2
 Since

∆𝑧 = 𝑊𝑆 = 𝑄 = 0

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 Therefore,

∆𝑢2
∆𝐻 + =0
2
∆𝑢2
𝐶𝑃 ∆𝑇 = −
2
𝑢2 2 − 𝑢1 2
𝐶𝑃 (𝑇2 − 𝑇1 ) = −
2
2 2
𝑢2 − 𝑢1
𝑇2 = − + 𝑇1
2𝐶𝑃
(502 − 2.52 ) ∗ 2 ∗ 𝑚2 ∗ 𝑚𝑜𝑙 ∗ 𝐾 28 𝑔 𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 𝐽 𝑁 ∗ 𝑠𝑒𝑐 2
𝑇2 = − ∗ ∗ ∗
2 ∗ 7 ∗ 8.314 𝐽 ∗ 𝑠𝑒𝑐 2 1 𝑚𝑜𝑙 𝑁𝑖𝑡𝑟𝑜𝑔𝑒𝑛 𝑁 ∗ 𝑚 𝑘𝑔 ∗ 𝑚
1 𝑘𝑔
∗ + 423.15 𝐾
1000 𝑔
𝑇2 = −1.199 𝐾 + 423.15 𝐾
𝑇2 = 421.95 𝐾
𝑇2 = (421.95 − 273.15) 0.𝐶
𝑻𝟐 = 𝟏𝟒𝟖. 𝟖 𝟎.𝑪 Answe𝑟

Problem 3.22:

One mole of an ideal gas, initially at 30 0C and 1 bar, is changed to 130 0C and 10 bars
by three different mechanically reversible processes:
a) The gas is first heated at constant volume until its temperature is 130 0C; then it
is compressed isothermally until its pressure is 10 bar
b) The gas is first heated at constant pressure until its temperature is 130 0C; then
it is compressed isothermally to 10 bar
c) The gas is first compressed isothermally to 10 bar; then it is heated at constant
pressure to 130 0C
Calculate Q, W, ∆𝑼 𝒂𝒏𝒅 ∆𝑯 in each case. Take CP = (7/2) R and CV = (5/2) R.
alternatively, take CP = (5/2) R and CV = (3/2) R

Given Data:

𝑇1 = 30 0.𝐶
𝑇1 = (30 + 273.15) 𝐾
𝑇1 = 303.15 𝐾
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𝑃1 = 1 𝑏𝑎𝑟
𝑇2 = 130 0.𝐶
𝑇3 = (130 + 273.15) 𝐾
𝑇3 = 403.15 𝐾
𝑃3 = 10 bar
𝑄 =?
𝑊 =?
∆𝑈 =?
∆𝐻 =?

Solution:
7
𝐶𝑃 = 𝑅
2
5
𝐶𝑉 = 𝑅
2

 Each part consist of two steps, 12 & 23


 For the overall processes

∆𝑈 = ∆𝑈12 = ∆𝑈23 = 𝐶𝑉 ∆𝑇
5
∆𝑈 = ∆𝑈12 = ∆𝑈23 = 𝑅 (𝑇3 − 𝑇1 )
2
5 𝐽 1 𝑘𝐽
∆𝑈 = ∆𝑈12 = ∆𝑈23 = ∗ 8.314 (403.15 − 303.15)𝐾 ∗
2 𝑚𝑜𝑙∗𝐾 1000 𝐽

𝒌𝑱
∆𝑼 = ∆𝑼𝟏𝟐 = ∆𝑼𝟐𝟑 = 𝟐. 𝟎𝟕𝟗 → (𝒂) Answe𝑟
𝒎𝒐𝒍

 Now

∆𝐻 = ∆𝐻12 = ∆𝐻23 = 𝐶𝑃 ∆𝑇
7
∆𝐻 = ∆𝐻12 = ∆𝐻23 = 𝑅(𝑇2 − 𝑇1 )
2
7 𝐽 𝑘𝐽
∆𝐻 = ∆𝐻12 = ∆𝐻23 = ∗ 8.314 (403.15 − 303.15)𝐾 ∗ 1
2 𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽
𝒌𝑱
∆𝑯 = ∆𝑯𝟏𝟐 = ∆𝑯𝟐𝟑 = 𝟐. 𝟗𝟏 → (𝒃)Answe𝑟
𝒎𝒐𝒍

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(a)

Step 12:
 For step “12” volume is constant
 Therefore

𝑾𝟏𝟐 = 𝟎
 Here

𝑇2 = 𝑇3
 According to first law of thermodynamics

∆𝑈12 = 𝑄12 + 𝑊12


∆𝑈12 = 𝑄12
𝑄12 = ∆𝑈12 = 𝐶𝑉 ∆𝑇
𝒌𝑱
𝑸𝟏𝟐 = ∆𝑼𝟏𝟐 = 𝟐. 𝟎𝟕𝟗 [𝑭𝒓𝒐𝒎 (𝒂)]
𝒎𝒐𝒍

 Also we have

𝒌𝑱
∆𝑯𝟏𝟐 = 𝟐. 𝟗𝟏 [𝑭𝒓𝒐𝒎 (𝒃)]
𝒎𝒐𝒍
Step 23:
 Since for step “23” process is isothermal
 Therefore
∆𝑼𝟐𝟑 = ∆𝑯𝟐𝟑 = 𝟎
 Here

𝑇2 = 𝑇3
 Now, intermediate pressure can be calculated as

𝑃1 𝑃2
=
𝑇1 𝑇2
𝑃1
𝑃2 = ∗𝑇
𝑇1 2
1 𝑏𝑎𝑟
𝑃2 = ∗ 403.15 𝐾
303.15 𝐾
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𝑃2 = 1.329 𝑏ar

 For an isothermal process we have


𝑃3
𝑊23 = 𝑅𝑇2 ln
𝑃2
𝐽 1 𝑘𝐽 10
𝑊23 = 8.314 ∗ 403.15 𝐾 ∗ ∗ ln
𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽 1.329
𝒌𝑱
𝑾𝟐𝟑 = 𝟔. 𝟕𝟔𝟒
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈23 = 𝑄23 + 𝑊23


0 = 𝑄23 + 𝑊23
𝑄23 = −𝑊23
𝒌𝑱
𝑸𝟐𝟑 = −𝟔. 𝟕𝟔𝟒
𝒎𝒐𝒍

 For the complete cycle,

𝑊𝑜𝑟𝑘 = 𝑊 = 𝑊12 + 𝑊23


𝑘𝐽
𝑊 = (0 + 6.764)
𝑚𝑜𝑙
𝒌𝑱
𝑾 = 𝟔. 𝟕𝟔𝟒 Answe𝑟
𝒎𝒐𝒍

𝑄 = 𝑄12 + 𝑄23
𝑘𝐽
𝑄 = (2.079 − 6.764)
𝑚𝑜𝑙
𝒌𝑱
𝑸 = −𝟒. 𝟔𝟖𝟓 Answe𝑟
𝒎𝒐𝒍

∆𝑈 = ∆𝑈12 + ∆𝑈23
𝑘𝐽
∆𝑈 = (2.079 + 0)
𝑚𝑜𝑙
𝒌𝑱
∆𝑼 = 𝟐. 𝟎𝟕𝟗 Answe𝑟
𝒎𝒐𝒍

∆𝐻 = ∆𝐻12 + ∆𝐻23
𝑘𝐽
∆𝐻 = (2.91 + 0)
𝑚𝑜𝑙
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𝒌𝑱
∆𝑯 = 𝟐. 𝟗𝟏 Answe𝑟
𝒎𝒐𝒍

(b)

Step 12:
 For step “12” volume is constant
 Therefore, at constant pressure we have

𝑘𝐽
𝑄12 = ∆𝐻12 = 2.91 [𝑭𝒓𝒐𝒎 (𝒃)]
𝑚𝑜𝑙

 Also,

𝒌𝑱
∆𝑼𝟏𝟐 = 𝟐. 𝟎𝟕𝟗 [𝑭𝒓𝒐𝒎 (𝒂)]
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈12 = 𝑄12 + 𝑊12


𝑊12 = ∆𝑈12 − 𝑄12
𝑘𝐽
𝑊12 = (2.079 − 2.91)
𝑚𝑜𝑙
𝒌𝑱
𝑾𝟏𝟐 = −𝟎. 𝟖𝟑𝟏
𝒎𝒐𝒍

Step 23:
 Since for step “23” process is isothermal ( T = Constant)
 Therefore
∆𝑼𝟐𝟑 = ∆𝑯𝟐𝟑 = 𝟎
 Here

𝑇2 = 𝑇3 & 𝑃1 = 𝑃2
 For an isothermal process we have
𝑃3
𝑊23 = 𝑅𝑇2 ln
𝑃2
𝐽 1 𝑘𝐽 10
𝑊23 = 8.314 ∗ 403.15 𝐾 ∗ ∗ ln
𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽 1
𝒌𝑱
𝑾𝟐𝟑 = 𝟕. 𝟕𝟏𝟖
𝒎𝒐𝒍

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 According to first law of thermodynamics

∆𝑈23 = 𝑄23 + 𝑊23


0 = 𝑄23 + 𝑊23
𝑄23 = −𝑊23
𝒌𝑱
𝑸𝟐𝟑 = −𝟕. 𝟕𝟏𝟖
𝒎𝒐𝒍

 For the complete cycle,

𝑊𝑜𝑟𝑘 = 𝑊 = 𝑊12 + 𝑊23


𝑘𝐽
𝑊 = (−0.831 + 7.718)
𝑚𝑜𝑙
𝒌𝑱
𝑾 = 𝟔. 𝟖𝟖𝟕 Answe𝑟
𝒎𝒐𝒍

𝑄 = 𝑄12 + 𝑄23
𝑘𝐽
𝑄 = (2.91 − 7.718)
𝑚𝑜𝑙
𝒌𝑱
𝑸 = −𝟒. 𝟖𝟎𝟖 Answe𝑟
𝒎𝒐𝒍

∆𝑈 = ∆𝑈12 + ∆𝑈23
𝑘𝐽
∆𝑈 = (2.079 + 0)
𝑚𝑜𝑙
𝒌𝑱
∆𝑼 = 𝟐. 𝟎𝟕𝟗 Answe𝑟
𝒎𝒐𝒍

∆𝐻 = ∆𝐻12 + ∆𝐻23
𝑘𝐽
∆𝐻 = (2.91 + 0)
𝑚𝑜𝑙
𝒌𝑱
∆𝑯 = 𝟐. 𝟗𝟏 Answe𝑟
𝒎𝒐𝒍

(c)

 Since for step “12” process is isothermal ( T = Constant)


 Therefore
∆𝑼𝟏𝟐 = ∆𝑯𝟏𝟐 = 𝟎
 Here

𝑃2 = 𝑃3

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 For an isothermal process we have


𝑃2
𝑊12 = 𝑅𝑇1 ln
𝑃1
𝐽 1 𝑘𝐽 10
𝑊12 = 8.314 ∗ 303.15 𝐾 ∗ ∗ ln
𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽 1
𝒌𝑱
𝑾𝟏𝟐 = 𝟓. 𝟖𝟎𝟑𝟒
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈12 = 𝑄12 + 𝑊12


0 = 𝑄12 + 𝑊12
𝑄12 = −𝑊12
𝒌𝑱
𝑸𝟏𝟐 = −𝟓. 𝟖𝟎𝟑𝟒
𝒎𝒐𝒍

Step 23:
 For step “23” volume is constant
 Therefore, at constant pressure we have

𝒌𝑱
𝑸𝟐𝟑 = ∆𝑯𝟐𝟑 = 𝟐. 𝟗𝟏 [𝑭𝒓𝒐𝒎 (𝒃)]
𝒎𝒐𝒍
 Here

𝑇2 = 𝑇3
 Now

𝒌𝑱
∆𝑼𝟐𝟑 = 𝟐. 𝟎𝟕𝟗 [𝑭𝒓𝒐𝒎 (𝒂)]
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈23 = 𝑄23 + 𝑊23


𝑊23 = ∆𝑈23 − 𝑄23
𝑘𝐽
𝑊23 = (2.079 − 2.91)
𝑚𝑜𝑙
𝒌𝑱
𝑊23 = −𝟎. 𝟖𝟑𝟏
𝒎𝒐𝒍

 For the complete cycle,

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𝑊𝑜𝑟𝑘 = 𝑊 = 𝑊12 + 𝑊23


𝑘𝐽
𝑊 = (5.8034 − 0.831)
𝑚𝑜𝑙
𝒌𝑱
𝑾 = 𝟒. 𝟗𝟕𝟐 Answe𝑟
𝒎𝒐𝒍

𝑄 = 𝑄12 + 𝑄23
𝑘𝐽
𝑄 = (−5.8034 + 2.91)
𝑚𝑜𝑙
𝒌𝑱
𝑸 = −𝟐. 𝟖𝟗𝟒 Answe𝑟
𝒎𝒐𝒍

∆𝑈 = ∆𝑈12 + ∆𝑈23
𝑘𝐽
∆𝑈 = (0 + 2.079)
𝑚𝑜𝑙
𝒌𝑱
∆𝑼 = 𝟐. 𝟎𝟕𝟗 Answe𝑟
𝒎𝒐𝒍

∆𝐻 = ∆𝐻12 + ∆𝐻23
𝑘𝐽
∆𝐻 = (0 + 2.91)
𝑚𝑜𝑙
𝒌𝑱
∆𝑯 = 𝟐. 𝟗𝟏 Answe𝑟
𝒎𝒐𝒍

Solution:
5
𝐶𝑃 = 𝑅
2
3
𝐶𝑉 = 𝑅
2

 Each part consist of two steps, 12 & 23


 For the overall processes

∆𝑈 = ∆𝑈12 = ∆𝑈23 = 𝐶𝑉 ∆𝑇
3
∆𝑈 = ∆𝑈12 = ∆𝑈23 = 𝑅 (𝑇3 − 𝑇1 )
2
3 𝐽 1 𝑘𝐽
∆𝑈 = ∆𝑈12 = ∆𝑈23 = ∗ 8.314 (403.15 − 303.15)𝐾 ∗
2 𝑚𝑜𝑙∗𝐾 1000 𝐽

𝒌𝑱
∆𝑼 = ∆𝑼𝟏𝟐 = ∆𝑼𝟐𝟑 = 𝟏. 𝟐𝟒𝟕 → (𝒂) Answe𝑟
𝒎𝒐𝒍
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 Now

∆𝐻 = ∆𝐻12 = ∆𝐻23 = 𝐶𝑃 ∆𝑇
5
∆𝐻 = ∆𝐻12 = ∆𝐻23 = 𝑅(𝑇2 − 𝑇1 )
2
5 𝐽 𝑘𝐽
∆𝐻 = ∆𝐻12 = ∆𝐻23 = ∗ 8.314 (403.15 − 303.15)𝐾 ∗ 1
2 𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽
𝒌𝑱
∆𝑯 = ∆𝑯𝟏𝟐 = ∆𝑯𝟐𝟑 = 𝟐. 𝟎𝟕𝟗 → (𝒃)Answe𝑟
𝒎𝒐𝒍

(a)

Step 12:
 For step “12” volume is constant
 Therefore

𝑾𝟏𝟐 = 𝟎
 Here

𝑇2 = 𝑇3
 According to first law of thermodynamics

∆𝑈12 = 𝑄12 + 𝑊12


∆𝑈12 = 𝑄12
𝑄12 = ∆𝑈12 = 𝐶𝑉 ∆𝑇
𝒌𝑱
𝑸𝟏𝟐 = ∆𝑼𝟏𝟐 = 𝟏. 𝟐𝟒𝟕 [𝑭𝒓𝒐𝒎 (𝒂)]
𝒎𝒐𝒍

 Also we have

𝒌𝑱
∆𝑯𝟏𝟐 = 𝟐. 𝟎𝟕𝟗 [𝑭𝒓𝒐𝒎 (𝒃)]
𝒎𝒐𝒍

Step 23:
 Since for step “23” process is isothermal

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 Therefore
∆𝑼𝟐𝟑 = ∆𝑯𝟐𝟑 = 𝟎
 Here

𝑇2 = 𝑇3
 Now, intermediate pressure can be calculated as

𝑃1 𝑃2
=
𝑇1 𝑇2
𝑃1
𝑃2 = ∗𝑇
𝑇1 2
1 𝑏𝑎𝑟
𝑃2 = ∗ 403.15 𝐾
303.15 𝐾
𝑃2 = 1.329 𝑏ar

 For an isothermal process we have


𝑃3
𝑊23 = 𝑅𝑇2 ln
𝑃2
𝐽 1 𝑘𝐽 10
𝑊23 = 8.314 ∗ 403.15 𝐾 ∗ ∗ ln
𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽 1.329
𝒌𝑱
𝑾𝟐𝟑 = 𝟔. 𝟕𝟔𝟒
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈23 = 𝑄23 + 𝑊23


0 = 𝑄23 + 𝑊23
𝑄23 = −𝑊23
𝒌𝑱
𝑸𝟐𝟑 = −𝟔. 𝟕𝟔𝟒
𝒎𝒐𝒍

 For the complete cycle,

𝑊𝑜𝑟𝑘 = 𝑊 = 𝑊12 + 𝑊23


𝑘𝐽
𝑊 = (0 + 6.764)
𝑚𝑜𝑙
𝒌𝑱
𝑾 = 𝟔. 𝟕𝟔𝟒 Answe𝑟
𝒎𝒐𝒍

𝑄 = 𝑄12 + 𝑄23
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𝑘𝐽
𝑄 = (1.247 − 6.764)
𝑚𝑜𝑙
𝒌𝑱
𝑸 = −𝟓. 𝟓𝟏𝟔 Answe𝑟
𝒎𝒐𝒍

∆𝑈 = ∆𝑈12 + ∆𝑈23
𝑘𝐽
∆𝑈 = (1.247 + 0)
𝑚𝑜𝑙
𝒌𝑱
∆𝑼 = 𝟏. 𝟐𝟒𝟕 Answe𝑟
𝒎𝒐𝒍

∆𝐻 = ∆𝐻12 + ∆𝐻23
𝑘𝐽
∆𝐻 = (2.079 + 0)
𝑚𝑜𝑙
𝒌𝑱
∆𝑯 = 𝟐. 𝟎𝟕𝟗 Answe𝑟
𝒎𝒐𝒍

(b)

Step 12:
 For step “12” volume is constant
 Therefore, at constant pressure we have

𝑘𝐽
𝑄12 = ∆𝐻12 = 2.079 [𝑭𝒓𝒐𝒎 (𝒃)]
𝑚𝑜𝑙

 Also,

𝒌𝑱
∆𝑼𝟏𝟐 = 𝟏. 𝟐𝟒𝟕 [𝑭𝒓𝒐𝒎 (𝒂)]
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈12 = 𝑄12 + 𝑊12


𝑊12 = ∆𝑈12 − 𝑄12
𝑘𝐽
𝑊12 = (1.247 − 2.079)
𝑚𝑜𝑙
𝒌𝑱
𝑾𝟏𝟐 = −𝟎. 𝟖𝟑𝟐
𝒎𝒐𝒍

Step 23:
 Since for step “23” process is isothermal ( T = Constant)

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 Therefore
∆𝑼𝟐𝟑 = ∆𝑯𝟐𝟑 = 𝟎
 Here

𝑇2 = 𝑇3 & 𝑃1 = 𝑃2
 For an isothermal process we have
𝑃3
𝑊23 = 𝑅𝑇2 ln
𝑃2
𝐽 1 𝑘𝐽 10
𝑊23 = 8.314 ∗ 403.15 𝐾 ∗ ∗ ln
𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽 1
𝒌𝑱
𝑾𝟐𝟑 = 𝟕. 𝟕𝟏𝟖
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈23 = 𝑄23 + 𝑊23


0 = 𝑄23 + 𝑊23
𝑄23 = −𝑊23
𝒌𝑱
𝑸𝟐𝟑 = −𝟕. 𝟕𝟏𝟖
𝒎𝒐𝒍

 For the complete cycle,

𝑊𝑜𝑟𝑘 = 𝑊 = 𝑊12 + 𝑊23


𝑘𝐽
𝑊 = (−0.832 + 7.718)
𝑚𝑜𝑙
𝒌𝑱
𝑾 = 𝟔. 𝟖𝟖𝟔 Answe𝑟
𝒎𝒐𝒍

𝑄 = 𝑄12 + 𝑄23
𝑘𝐽
𝑄 = (2.079 − 7.718)
𝑚𝑜𝑙
𝒌𝑱
𝑸 = −𝟓. 𝟔𝟑𝟗 Answe𝑟
𝒎𝒐𝒍

∆𝑈 = ∆𝑈12 + ∆𝑈23
𝑘𝐽
∆𝑈 = (1.247 + 0)
𝑚𝑜𝑙
𝒌𝑱
∆𝑼 = 𝟏. 𝟐𝟒𝟕 Answe𝑟
𝒎𝒐𝒍

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∆𝐻 = ∆𝐻12 + ∆𝐻23
𝑘𝐽
∆𝐻 = (2.079 + 0)
𝑚𝑜𝑙
𝒌𝑱
∆𝑯 = 𝟐. 𝟎𝟕𝟗 Answe𝑟
𝒎𝒐𝒍

(c)

Step 12:
 Since for step “12” process is isothermal ( T = Constant)
 Therefore
∆𝑼𝟏𝟐 = ∆𝑯𝟏𝟐 = 𝟎
 Here

𝑃2 = 𝑃3
 For an isothermal process we have
𝑃2
𝑊12 = 𝑅𝑇1 ln
𝑃1
𝐽 1 𝑘𝐽 10
𝑊12 = 8.314 ∗ 303.15 𝐾 ∗ ∗ ln
𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽 1
𝒌𝑱
𝑾𝟏𝟐 = 𝟓. 𝟖𝟎𝟑𝟒
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈12 = 𝑄12 + 𝑊12


0 = 𝑄12 + 𝑊12
𝑄12 = −𝑊12
𝒌𝑱
𝑸𝟏𝟐 = −𝟓. 𝟖𝟎𝟑𝟒
𝒎𝒐𝒍

Step 23:
 For step “23” volume is constant
 Therefore, at constant pressure we have

𝒌𝑱
𝑸𝟐𝟑 = ∆𝑯𝟐𝟑 = 𝟐. 𝟎𝟕𝟗 [𝑭𝒓𝒐𝒎 (𝒃)]
𝒎𝒐𝒍
 Here

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𝑇2 = 𝑇3
 Now

𝒌𝑱
∆𝑼𝟐𝟑 = 𝟏. 𝟐𝟒𝟕 [𝑭𝒓𝒐𝒎 (𝒂)]
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈23 = 𝑄23 + 𝑊23


𝑊23 = ∆𝑈23 − 𝑄23
𝑘𝐽
𝑊23 = (1.247 − 2.079)
𝑚𝑜𝑙
𝒌𝑱
𝑊23 = −𝟎. 𝟖𝟑𝟐
𝒎𝒐𝒍

 For the complete cycle,

𝑊𝑜𝑟𝑘 = 𝑊 = 𝑊12 + 𝑊23


𝑘𝐽
𝑊 = (5.8034 − 0.832)
𝑚𝑜𝑙
𝒌𝑱
𝑾 = 𝟒. 𝟗𝟕𝟏𝟒 Answe𝑟
𝒎𝒐𝒍

𝑄 = 𝑄12 + 𝑄23
𝑘𝐽
𝑄 = (−5.8034 + 2.079)
𝑚𝑜𝑙
𝒌𝑱
𝑸 = −𝟑. 𝟕𝟐𝟒 Answe𝑟
𝒎𝒐𝒍

∆𝑈 = ∆𝑈12 + ∆𝑈23
𝑘𝐽
∆𝑈 = (0 + 1.247)
𝑚𝑜𝑙
𝒌𝑱
∆𝑼 = 𝟏. 𝟐𝟒𝟕 Answe𝑟
𝒎𝒐𝒍

∆𝐻 = ∆𝐻12 + ∆𝐻23
𝑘𝐽
∆𝐻 = (0 + 2.079)
𝑚𝑜𝑙
𝒌𝑱
∆𝑯 = 𝟐. 𝟎𝟕𝟗 Answe𝑟
𝒎𝒐𝒍

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Problem 3.23:

One mole of an ideal gas, initially at 30 ℃ and 1 bars, undergoes the following
mechanically reversible changes. It is compressed isothermally to point such that when
it is heated at constant volume to 120 ℃ its final pressure is 12 bars. Calculate Q, W,
∆𝑼 𝒂𝒏𝒅 ∆𝑯 for the process. Take CP = (7/2) R and CV = (5/2) R.

Given Data:

𝑇1 = 30 ℃
𝑇1 = (30 + 273.15) 𝐾
𝑇1 = 303.15 𝐾
𝑃1 = 1 𝑏𝑎𝑟
𝑇3 = 120 ℃
𝑇3 = (120 + 273.15) 𝐾
𝑇3 = 393.15 𝐾
𝑃3 = 12 𝑏𝑎𝑟
𝑄 =?
𝑊 =?
∆𝑈 =?
∆𝐻 =?
7
𝐶𝑃 = 𝑅
2
5
𝐶𝑉 = 𝑅
2

Solution:
 The process consist of two steps, 12 & 23

Step 12:
 Since for step “12” process is isothermal ( T = Constant)
 Therefore

∆𝑼𝟏𝟐 = ∆𝑯𝟏𝟐 = 𝟎
 Now, intermediate pressure can be calculated as

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𝑃2 𝑃3
=
𝑇2 𝑇3
𝑃3
𝑃2 = ∗𝑇
𝑇3 2
12 𝑏𝑎𝑟
𝑃2 = ∗ 303.15 𝐾
393.15 𝐾
𝑃2 = 9.25 𝑏ar

 For an isothermal process we have


𝑃2
𝑊12 = 𝑅𝑇1 ln
𝑃1
𝐽 1 𝑘𝐽 9.25
𝑊12 = 8.314 ∗ 303.15.15 𝐾 ∗ ∗ ln
𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽 1
𝒌𝑱
𝑾𝟏𝟐 = 𝟓. 𝟔𝟎𝟕
𝒎𝒐𝒍

 According to first law of thermodynamics

∆𝑈12 = 𝑄12 + 𝑊12


0 = 𝑄12 + 𝑊12
𝑄12 = −𝑊12
𝒌𝑱
𝑸𝟏𝟐 = −𝟓. 𝟔𝟎𝟕
𝒎𝒐𝒍

Step 23:
 Since for step “23” volume is constant
 Therefore

𝑾𝟐𝟑 = 𝟎
 According to first law of thermodynamics

∆𝑈23 = 𝑄23 + 𝑊23


∆𝑈23 = 𝑄23

𝑄23 = ∆𝑈23 = 𝐶𝑉 ∆𝑇
5
𝑄23 = ∆𝑈23 = 𝑅 (𝑇3 − 𝑇1 )
2

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5 𝐽 1 𝑘𝐽
𝑄23 = ∆𝑈23 = ∗ 8.314 (393.15 − 303.15)𝐾 ∗
2 𝑚𝑜𝑙∗𝐾 1000 𝐽
𝒌𝑱
𝑸𝟐𝟑 = ∆𝑼𝟐𝟑 = 𝟏. 𝟖𝟕𝟏
𝒎𝒐𝒍

 Now

∆𝐻23 = 𝐶𝑃 ∆𝑇
7
∆𝐻23 = 𝑅(𝑇2 − 𝑇1 )
2
7 𝐽 𝑘𝐽
∆𝐻23 = ∗ 8.314 (393.15 − 303.15)𝐾 ∗ 1
2 𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽
𝒌𝑱
∆𝐻23 = 𝟐. 𝟔𝟏𝟗
𝒎𝒐𝒍

 For the complete cycle,

𝑊𝑜𝑟𝑘 = 𝑊 = 𝑊12 + 𝑊23


𝑘𝐽
𝑊 = (5.607 + 0)
𝑚𝑜𝑙
𝒌𝑱
𝑾 = 𝟓. 𝟔𝟎𝟕 Answe𝑟
𝒎𝒐𝒍

𝑄 = 𝑄12 + 𝑄23
𝑘𝐽
𝑄 = (−5.607 + 1.871)
𝑚𝑜𝑙
𝒌𝑱
𝑸 = −𝟑. 𝟕𝟑𝟔 Answe𝑟
𝒎𝒐𝒍

∆𝑈 = ∆𝑈12 + ∆𝑈23
𝑘𝐽
∆𝑈 = (0 + 1.871)
𝑚𝑜𝑙
𝒌𝑱
∆𝑼 = 𝟏. 𝟖𝟕𝟏 Answe𝑟
𝒎𝒐𝒍

∆𝐻 = ∆𝐻12 + ∆𝐻23
𝑘𝐽
∆𝐻 = (0 + 2.691)
𝑚𝑜𝑙
𝒌𝑱
∆𝑯 = 𝟐. 𝟔𝟗𝟏 Answe𝑟
𝒎𝒐𝒍

Problem 3.24:

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A process consists of two steps: (1) One mole of air at T = 800 K and P = 4 bars are
cooled at constant volume to T = 350 K. (2) The air is then heated air constant pressure
until its temperature reaches 800 K. If this two step process is replaced by a single
isothermal expansion of the air from 800 K and 4 bar to some final pressure P, what is
the value of P that makes the work of two step processes the same? Assume mechanical
reversibility and treat air as an ideal gas with CP = (7/2) R and CV = (5/2) T.

Given Data:

𝑇1 = 800 𝐾
𝑃1 = 4 𝑏𝑎𝑟
𝑇2 = 350 𝐾
𝑃 =?

Solution:
 For the first step volume is constant
 Therefore,

𝑊12 = 0
 For the work done is

𝑊 = 𝑊23 = −𝑃2 ∆𝑉 → (1)


 For one mole of an ideal gas we have,

𝑃∆𝑉 = 𝑅∆𝑇
𝑃2 ∆𝑉 = 𝑅∆𝑇
 Put in (1)

𝑊 = −𝑅∆𝑇
𝑊 = −𝑅(𝑇3 − 𝑇2 )
 Since
𝑇3 = 𝑇1
 Therefore

𝑊 = −𝑅(𝑇1 − 𝑇2 ) → (2)
 For an isothermal process we have
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𝑃
𝑊 = 𝑅𝑇1 ln → (3)
𝑃1
 Compare (2) and (3)

𝑃
−𝑅(𝑇1 − 𝑇2 ) = 𝑅𝑇1 ln
𝑃1
𝑃
𝑇2 − 𝑇1 = 𝑇1 ln
𝑃1
𝑇2 − 𝑇1 𝑃
= ln
𝑇1 𝑃1
(350 − 800) 𝐾 𝑃
= ln
800 𝐾 4 𝑏𝑎𝑟
𝑃
𝑒 −0.5625 =
4 𝑏𝑎𝑟
4 𝑏𝑎𝑟 ∗ 0.5698 = 𝑃
𝑷 = 𝟐. 𝟐𝟕𝟗 𝒃𝒂𝒓 Answe𝑟

Problem 3.25:

A scheme for finding the internal volume 𝑽𝒕𝑩 of the gas cylinder consists of the following
steps. The cylinder is filled with a gas to low pressure P1, and connected through a small
line and valve to an evacuated reference tank of known volume𝑽𝒕𝑨 . The valve is opened,
and the gas flows through the line into the reference tank. After the system returns to its
initial temperature, a sensitive pressure transducer provides a valve for the pressure
change ∆𝑷 in the cylinder. Determine the cylinder volume 𝑽𝒕𝑩 from the following data:
a) 𝑽𝒕𝑨 = 𝟐𝟓𝟔 𝒄𝒎𝟑
b) ∆𝑷⁄𝑷𝟏 = −𝟎. 𝟎𝟔𝟑𝟗

Given Data:

𝑉𝐵𝑡 =?
𝑉𝐴𝑡 = 256 𝑐𝑚3
∆𝑃
= −0.0639
𝑃1

Solution:
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∆𝑃
= −0.0639
𝑃1
𝑃2 − 𝑃1
= −0.0639
𝑃1
𝑃2
− 1 = −0.0639
𝑃1
𝑃2
= −0.0639 + 1
𝑃1
𝑃2
= 0.9361 → (1)
𝑃1
 Assume that gas is ideal & P2 is the pressure of the tank
 When gas flows through the line into the tank then tank’s total volume becomes 𝑉𝐴𝑡 + 𝑉𝐵𝑡
 Now, by applying condition for an ideal gas

𝑃1 𝑉𝐵𝑡 = 𝑃2 (𝑉𝐴𝑡 + 𝑉𝐵𝑡 )


𝑃2 𝑉𝐵𝑡
=
𝑃1 𝑉𝐴𝑡 +𝑉𝐵𝑡

 Put in (1)

𝑉𝐵𝑡
= 0.9361
𝑉𝐴𝑡 + 𝑉𝐵𝑡
𝑉𝐵𝑡 = 0.9361(𝑉𝐴𝑡 + 𝑉𝐵𝑡 )
𝑉𝐵𝑡 = 0.9361𝑉𝐴𝑡 + 0.9361𝑉𝐵𝑡
𝑉𝐵𝑡 − 0.9361𝑉𝐵𝑡 = 0.9361𝑉𝐴𝑡
𝑉𝐵𝑡 (1 − 0.9361) = 0.9361𝑉𝐴𝑡
0.0639𝑉𝐵𝑡 = 256 𝑐𝑚3 ∗ 0.9361
239.6461 3
𝑉𝐵𝑡 = 𝑐𝑚
0.0639
𝑽𝒕𝑩 = 𝟑𝟕𝟓𝟎. 𝟐𝟔 𝒄𝒎𝟑 Answe𝑟

Problem 3.26:

A closed, non-conducting, horizontal cylinder is fitted with non-conducting, frictionless,


floating piston which divides the cylinder in two Sections A & B. The two sections
contains equal masses of air, initially at the same conditions, T1 = 300 K and

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P1 = 1 atm. An electrical heating element in section A is activated, and the air


temperature slowly increases: TA in section A because of heat transfer, and TB in section
B because of adiabatic compression by slowly moving piston. Treat air as an ideal gas
with CP = (7/2) R and let nA be the number of moles of air in section A. For the process
as described, evaluate one of the following sets of quantities:
a) TA, TB, and Q/ nA, if P (final) = 1.25 atm
b) TB, Q/ nA, and P (final), if TA = 425 K
c) TA, Q/nA, and P (final), if TB = 325 K
d) TA, TB, and P (final), if Q/nA = 3 kJ mol-1.

Given Data:

𝑇1 = 300 𝐾
𝑃1 = 1 𝑎𝑡𝑚
7
𝐶𝑃 = 𝑅
2

Solution:
 According to ideal gas equation,

𝑃𝑉 = 𝑛𝑅𝑇
 Applying ideal gas equation for initial conditions
 On section “A”
𝑃1 𝑉𝐴 = 𝑛𝐴 𝑅𝑇1
𝑛𝐴 𝑅𝑇1
𝑉𝐴 =
𝑃1
 On section “B”
𝑃1 𝑉𝐵 = 𝑛𝐵 𝑅𝑇1
 Since

𝑛𝐴 = 𝑛𝐵
 Therefore,
𝑃1 𝑉𝐵 = 𝑛𝐴 𝑅𝑇1
𝑛𝐴 𝑅𝑇1
𝑉𝐵 =
𝑃1
 Total initial volume can be given as

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𝑉𝑖 = 𝑉𝐴 + 𝑉𝐵
𝑛𝐴 𝑅𝑇1 𝑛𝐴 𝑅𝑇1
𝑉𝑖 = +
𝑃1 𝑃1
𝑛𝐴 𝑅𝑇1
𝑉𝑖 = 2.
𝑃1

 Let P2 be the final pressure & TA & TB are the final temperatures of section A & section B
respectively
 Applying ideal gas equation for final conditions
 On section “A”
𝑃2 𝑉𝐴 = 𝑛𝐴 𝑅𝑇𝐴

𝑛𝐴 𝑅𝑇𝐴
𝑉𝐴 =
𝑃2
 On section “B”
𝑃2 𝑉𝐵 = 𝑛𝐴 𝑅𝑇𝐵
𝑛𝐴 𝑅𝑇𝐵
𝑉𝐵 =
𝑃2
 Total Final volume can be given as

𝑉𝑓 = 𝑉𝐴 + 𝑉𝐵
𝑛𝐴 𝑅𝑇𝐴 𝑛𝐴 𝑅𝑇𝐵
𝑉𝑓 = +
𝑃2 𝑃2
𝑛𝐴 𝑅(𝑇𝐴 + 𝑇𝐵 )
𝑉𝑓 =
𝑃2
 Since the total volume is constant, therefore

𝑉𝑖 = 𝑉𝑓

𝑛𝐴 𝑅𝑇1 𝑛𝐴 𝑅(𝑇𝐴 +𝑇𝐵 )


2. =
𝑃1 𝑃2
𝟐.𝑻𝟏 (𝑻𝑨 +𝑻𝑩 )
= → (1)
𝑷𝟏 𝑷𝟐

(a)

𝑃2 = 1.25 𝑎𝑡𝑚

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 Since the process occurring in section B is reversible adiabatic compression


 Therefore, for an adiabatic compression we have

1−𝛾 1−𝛾
𝑇1 (𝑃1 ) 𝛾 = 𝑇𝐵 (𝑃2 ) 𝛾
1−𝛾
𝑇1 (𝑃1 ) 𝛾
𝑇𝐵 = 1−𝛾
(𝑃2 ) 𝛾

𝛾−1
𝑃2 𝛾
𝑇𝐵 = 𝑇1 ( ) → (2)
𝑃 1

 We know that,
𝐶𝑃 − 𝐶𝑉 = 𝑅
𝐶𝑉 = 𝐶𝑃 − 𝑅
7
𝐶𝑉 = 𝑅 − 𝑅
2
7𝑅 − 2𝑅
𝐶𝑉 =
2
5
𝐶𝑉 = 𝑅
2
 As

𝐶𝑃
𝛾=
𝐶𝑉
7∗𝑅∗2
𝛾=
2∗5∗𝑅
𝛾 = 1.4
 Put in (2)

1.4−1
1.25 1.4
𝑇𝐵 = 300 𝐾 ( )
1
𝑇𝐵 = 300 𝐾 ∗ 1.0658

𝑻𝑩 = 𝟑𝟏𝟗. 𝟕𝟒𝑲 Answe𝑟

 Put in (1)

2∗300 𝐾 (𝑇𝐴 +319.74 𝐾)


=
1 𝑎𝑡𝑚 1.25 𝑎𝑡𝑚

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600 𝐾 ∗ 1.25 = 𝑇𝐴 + 319.74 𝐾


𝑇𝐴 = 750 𝐾 − 319.74 𝐾
𝑇𝐴 = 430.26 𝐾 Answe𝑟
 According to first law of thermodynamics

∆𝑈 = 𝑄 + 𝑊
 Since volume is constant, therefore

∆𝑈 = 𝑄 → (𝑎)
 For section A & B
∆𝑈 = ∆𝑈𝐴 + ∆𝑈𝐵
 Put in (a)

𝑄 = ∆𝑈𝐴 + ∆𝑈𝐵
𝑄 = 𝑛𝐴 𝐶𝑉 ∆𝑇 + 𝑛𝐴 𝐶𝑉 ∆𝑇
𝑄 = 𝑛𝐴 𝐶𝑉 (𝑇𝐴 − 𝑇1 ) + 𝑛𝐴 𝐶𝑉 (𝑇𝐵 − 𝑇1 )
𝑄 = 𝑛𝐴 𝐶𝑉 [𝑇𝐴 − 𝑇1 + 𝑇𝐵 − 𝑇1 ]
𝑄 = 𝑛𝐴 𝐶𝑉 [𝑇𝐴 + 𝑇𝐵 − 2𝑇1 ]
𝑄
= 𝐶𝑉 [𝑇𝐴 + 𝑇𝐵 − 2𝑇1 ] → (3)
𝑛𝐴
𝑄 5
= 𝑅(430.26 + 319.74 − 2 ∗ 300) 𝐾
𝑛𝐴 2
𝑄 5 𝐽 1𝑘𝐽
= ∗ 8.314 ∗ 150.02 𝐾 ∗
𝑛𝐴 2 𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽
𝑸 𝒌𝑱
= 𝟑. 𝟏𝟏𝟖 Answe𝑟
𝒏𝑨 𝒎𝒐𝒍

(b)

𝑇𝐴 = 425 𝐾
 From equation (1)

2. 𝑇1 (𝑇𝐴 + 𝑇𝐵 )
=
𝑃1 𝑃2
𝑃2 (𝑇𝐴 +𝑇𝐵 )
=
𝑃1 2.𝑇1

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 Put in (2)

𝛾−1
𝑇𝐴 + 𝑇𝐵 𝛾
𝑇𝐵 = 𝑇1 ( )
2. 𝑇1
 Assume 𝑇𝐵 = 319 𝐾

1.4−1
425 + 319 1.4
𝑇𝐵 = 300 𝐾 ( )
2 ∗ 300
𝑇𝐵 = 300𝐾 ∗ (1.0634)
𝑇𝐵 = 319.02 𝐾
 Since 319 ≈ 319.02, therefore

𝑻𝑩 = 𝟑𝟏𝟗. 𝟎𝟐 𝑲 Answe𝑟

 Put in (1)

2∗300 𝐾 (425+319.02) 𝐾
=
1 𝑎𝑡𝑚 𝑃2
744.02
𝑃2 = 𝑎𝑡𝑚
600
𝑷𝟐 = 𝟏. 𝟐𝟒 𝒂𝒕𝒎 Answe𝑟
 From equation (3)

𝑄
= 𝐶𝑉 [𝑇𝐴 + 𝑇𝐵 − 2𝑇1 ]
𝑛𝐴

𝑄 5
= 𝑅(425 + 319.02 − 2 ∗ 300) 𝐾
𝑛𝐴 2
𝑄 5 𝐽 1𝑘𝐽
= ∗ 8.314 ∗ 144.02 𝐾 ∗
𝑛𝐴 2 𝑚𝑜𝑙∗𝐾 1000 𝐽
𝑄 𝑘𝐽
= 2.993 Answe𝑟
𝑛𝐴 𝑚𝑜𝑙

(c)

𝑇𝐵 = 325 𝐾
 Put in (2)

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𝛾−1
𝑃2 𝛾
𝑇𝐵 = 𝑇1 ( )
𝑃 1
𝛾−1
𝑃2 𝛾
325 𝐾 = 300 𝐾 ( )
1 𝑎𝑡𝑚
𝛾−1
325 𝑃2 𝛾
=( )
300 1 𝑎𝑡𝑚
𝛾
325 𝛾−1 𝑃2
( ) =
300 1 𝑎𝑡𝑚
1.4
325 1.4−1
𝑃2 = ( ) 𝑎𝑡𝑚
300
𝑷𝟐 = 𝟏. 𝟑𝟐𝟑 𝒂𝒕𝒎 Answe𝑟
 Put in (1)

2.𝑇1 (𝑇𝐴 +𝑇𝐵 )


=
𝑃1 𝑃2
2 ∗ 300 𝐾 𝑇𝐴 + 325 𝐾
=
1 𝑎𝑡𝑚 1.323 𝑎𝑡𝑚
𝑇𝐴 + 325 𝐾 = 600 𝐾 ∗ 1.323
𝑇𝐴 = 793.9 𝐾 − 325 𝐾
𝑻𝑨 = 𝟒𝟔𝟖. 𝟗 𝑲 Answe𝑟
 From equation (3)

𝑄
= 𝐶𝑉 [𝑇𝐴 + 𝑇𝐵 − 2𝑇1 ]
𝑛𝐴

𝑄 5
= 𝑅(468.9 + 325 − 2 ∗ 300) 𝐾
𝑛𝐴 2
𝑄 5 𝐽 1𝑘𝐽
= ∗ 8.314 ∗ 193.9 𝐾 ∗
𝑛𝐴 2 𝑚𝑜𝑙∗𝐾 1000 𝐽
𝑄 𝑘𝐽
= 𝟒. 𝟎𝟑𝟎𝟐 Answe𝑟
𝑛𝐴 𝑚𝑜𝑙

(d)

𝑄 𝑘𝐽
=3
𝑛𝐴 𝑚𝑜𝑙

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 From equation (1)

2. 𝑇1 (𝑇𝐴 + 𝑇𝐵 )
=
𝑃1 𝑃2
2. 𝑇1 ∗ 𝑃2
𝑇𝐴 + 𝑇𝐵 = → (𝑏)
𝑃1
 From equation (3)

𝑄
= 𝐶𝑉 [𝑇𝐴 + 𝑇𝐵 − 2𝑇1 ]
𝑛𝐴
𝑄
𝑇𝐴 + 𝑇𝐵 − 2𝑇1 =
𝑛𝐴 ∗ 𝐶𝑉
𝑄
𝑇𝐴 + 𝑇𝐵 = + 2𝑇1 → (𝑐)
𝑛𝐴 ∗𝐶𝑉

 Comparing (b) and (c)

2. 𝑇1 ∗ 𝑃2 𝑄
= + 2𝑇1
𝑃1 𝑛𝐴 ∗ 𝐶𝑉
𝑃1 𝑄
𝑃2 = [ + 2𝑇1 ]
2.𝑇1 𝑛𝐴 ∗𝐶𝑉
1 𝑎𝑡𝑚 2 ∗ 3 𝑘𝐽
𝑃2 = [ + 2 ∗ 300 𝐾]
2 ∗ 300 𝐾 5𝑅 ∗ 𝑚𝑜𝑙
1 𝑎𝑡𝑚 6 𝑘𝐽 ∗ 𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽
𝑃2 = [ ∗ + 600𝐾]
600 𝐾 5 ∗ 𝑚𝑜𝑙 ∗ 8.314 𝐽 1 𝑘𝐽

1 𝑎𝑡𝑚
𝑃2 = [144.335 + 600] 𝐾
600 𝐾
𝑃2 = 1.2406 𝑎𝑡𝑚 Answe𝑟

 Put in (2)

𝛾−1
𝑃2 𝛾
𝑇𝐵 = 𝑇1 ( )
𝑃1
1.4−1
1.2406 1.4
𝑇𝐵 = 300 𝐾 ( )
1
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𝑇𝐵 = 300 𝐾 ∗ 1.0635

𝑻𝑩 = 𝟑𝟏𝟗. 𝟎𝟔 𝑲 Answe𝑟

 Put in (1)

2. 𝑇1 (𝑇𝐴 + 𝑇𝐵 )
=
𝑃1 𝑃2
2∗300 𝐾 (𝑇𝐴 +319.06 𝐾)
=
1 𝑎𝑡𝑚 1.2406 𝑎𝑡𝑚

600 𝐾 ∗ 1.2406 = 𝑇𝐴 + 319.06 𝐾


𝑇𝐴 = 744.36 𝐾 − 319.06 𝐾
𝑇𝐴 = 425.3𝐾 Answe𝑟

Problem 3.27:

One mole of an ideal gas with constant heat capacities undergoes an arbitrary
mechanically reversible process. Show that:
𝟏
∆𝑼 = 𝜸−𝟏 ∆(𝑷𝑽)

Given Data:

𝑁𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 = 𝑛 = 1

Solution:
 We know that

∆𝑈 = 𝑛𝐶𝑉 ∆𝑇
∆𝑈 = 1. 𝐶𝑉 ∆𝑇
∆𝑈 = 𝐶𝑉 (𝑇2 − 𝑇1 ) → (1)
 For an ideal gas we have,
𝐶𝑃 − 𝐶𝑉 = 𝑅
𝐶𝑃 𝐶𝑉 𝑅
− =
𝐶𝑉 𝐶𝑉 𝐶𝑉
𝐶𝑃 𝑅
−1=
𝐶𝑉 𝐶𝑉
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 Since

𝐶𝑃
𝛾=
𝐶𝑉

 Therefore,

𝑅
𝛾−1=
𝐶𝑉
𝑅
𝐶𝑉 =
𝛾−1

 Put in (1)

𝑅
∆𝑈 = (𝑇 − 𝑇1 )
𝛾−1 2
1
∆𝑈 = (𝑅𝑇2 − 𝑅𝑇1 ) → (2)
𝛾−1

 For one mole of an ideal gas we have

𝑃1 𝑉1 = 𝑅𝑇1 → (𝑎)
𝑃2 𝑉2 = 𝑅𝑇2 → (𝑏)
 Put (a) & (b) in (2)

1
∆𝑈 = (𝑃 𝑉 − 𝑃1 𝑉1 )
𝛾−1 2 2
1
∆𝑈 = ∆(𝑃𝑉) Proved
𝛾−1

Problem 3.28:

Derive an equation for the work of a mechanically reversible, isothermal compression


of 1 mole of a gas from an initial pressure p1 to a final pressure p2 when the equation
of state is the virial expansion truncated to:
𝒁 = 𝟏 + 𝑩′𝑷
How does the result compare with the corresponding equation for an ideal gas?

Solution:

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 For a mechanically reversible process we have,

𝑉
𝑊 = − ∫𝑉 2 𝑃𝑑𝑉 → (1)
1

 Given that

𝑍 = 1 + 𝐵′𝑃
 Also

𝑃𝑉
𝑍=
𝑅𝑇

 Therefore,

𝑃𝑉
= 1 + 𝐵′ 𝑃
𝑅𝑇
𝑅𝑇
𝑉= (1 + 𝐵′ 𝑃)
𝑃
1
𝑉 = 𝑅𝑇 ( + 𝐵′)
𝑃

 Differentiate both sides w.r.t to pressure

𝑑𝑉 −1
= 𝑅𝑇 ( 2 + 0)
𝑑𝑃 𝑃
𝑅𝑇
𝑑𝑉 = − 2 𝑑𝑃
𝑃

 Put in (1)

𝑉2
𝑊 = − ∫ 𝑃𝑑𝑉
𝑉1
𝑃2
𝑅𝑇
𝑊 = − ∫ −𝑃 𝑑𝑃
𝑃1 𝑃2
𝑃2
1
𝑊 = 𝑅𝑇 ∫ 𝑑𝑃
𝑃1 𝑃
𝑃
𝑊 = 𝑅𝑇|ln 𝑃|𝑃21
𝑊 = 𝑅𝑇(ln 𝑃2 − ln 𝑃1 )
𝑷𝟐
𝑾 = 𝑹𝑻 𝐥𝐧 Proved
𝑷𝟏

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Problem 3.30:

For methyl chloride at 100℃ the second and third virial coefficients are:
𝑩 = −𝟐𝟒𝟐. 𝟓𝒄𝒎𝟑 𝒎𝒐𝒍−𝟏 ; 𝑪 = 𝟐𝟓 𝟐𝟎𝟎 𝒄𝒎𝟔 𝒎𝒐𝒍−𝟐 .
Calculate the work of mechanically reversible, isothermal compression of 1 mol of
methyl chloride 1 bar to 55 bars at 100℃. Base calculations on the following forms of
virial equations
𝑩 𝑪
a) 𝒁 = 𝟏 + 𝑽 + 𝑽𝟐
b) 𝒁 = 𝟏 + 𝑩′ 𝑷 + 𝑪′𝑷𝟐
𝑩 𝑪−𝑩𝟐
Where 𝑩′ = 𝑹𝑻 & 𝑪′ = (𝑹𝑻)𝟐
Why don’t both equations give exactly the same result?

Given Data:

𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇 = 100 ℃
𝑇 = (100 + 273.15)𝐾
𝑇 = 373.15 𝐾
𝐵 = −242.5 𝑐𝑚3 𝑚𝑜𝑙 −1
𝐶 = 25200 𝑐𝑚6 𝑚𝑜𝑙−2
𝑃1 = 1 𝑏𝑎𝑟
𝑃2 = 55 𝑏𝑎𝑟
𝐵
𝐵′ =
𝑅𝑇

𝐶 − 𝐵2
𝐶 =
(𝑅𝑇)2
𝑊 =?

Solution:
 As

𝐵
𝐵′ =
𝑅𝑇
3

−242.5 𝑐𝑚 ∗ 𝑚𝑜𝑙 ∗ 𝐾 𝐽 101325 𝑁 1 𝑚3
𝐵 = ∗ ∗ ∗
𝑚𝑜𝑙 ∗ 8.314 𝐽 ∗ 373.15 𝐾 𝑁 ∗ 𝑚 𝑚2 ∗ 1.01325 𝑏𝑎𝑟 1003 𝑐𝑚3
𝟏
𝑩′ = −𝟕. 𝟖𝟏𝟕 ∗ 𝟏𝟎−𝟑
𝒃𝒂𝒓

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 Now,

𝐶−𝐵2
𝐶 ′ = (𝑅𝑇)2
[25200 − (−242.5)2 ]𝑐𝑚6 ∗ 𝐾 2 ∗ 𝑚𝑜𝑙 2

𝐽2 1013252 𝑁 2
𝐶 = ∗ 2 ∗
𝑚𝑜𝑙 2 ∗ 8.3142 𝐽2 ∗ 373.152 𝐾 2 𝑁 ∗ 𝑚2 𝑚4 ∗ 1.013252 𝑏𝑎𝑟 2
1 𝑚6

1006 𝑐𝑚6
𝟏
𝑪′ = −𝟑. 𝟒𝟗𝟐 ∗ 𝟏𝟎−𝟓 𝟐
𝒃𝒂𝒓

(a)

𝐵 𝐶
𝑍 =1+
+
𝑉 𝑉2
𝑃𝑉 𝐵 𝐶
=1+ + 2
𝑅𝑇 𝑉 𝑉
𝑅𝑇 𝐵 𝐶
𝑃 = (1 + + 2) → (1)
𝑉 𝑉 𝑉

 For a mechanically reversible process we have,

𝑉
𝑊 = − ∫𝑉 2 𝑃𝑑𝑉 → (2)
1

 Put (1) in (2)

𝑉2
𝑅𝑇 𝐵 𝐶
𝑊 = −∫ (1 + + 2 ) 𝑑𝑉
𝑉1 𝑉 𝑉 𝑉
𝑉2
𝐵 𝐶 1
𝑊 = −𝑅𝑇 ∫ (1 + + ) 𝑑𝑉 → (3)
𝑉1 𝑉 𝑉2 𝑉

 Again using

𝑅𝑇 𝐵 𝐶
𝑉1 =
𝑃1
(1 + 𝑉 + 𝑉 2 ) → (4)
1 1

 Assume that
𝑐𝑚3
𝑉1 = 30780 → (𝑎)
𝑚𝑜𝑙

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𝑅𝑇 8.314 𝐽∗373.15 𝐾 𝑁∗𝑚 1.01325 𝑏𝑎𝑟∗𝑚2 1003 ∗𝑐𝑚3


𝑃1
= 𝑚𝑜𝑙∗𝐾∗1 𝑏𝑎𝑟
∗ 𝐽
∗ 101325 𝑁
∗ 1 𝑚3
𝑅𝑇 𝑐𝑚3
= 31023.6 → (𝑏)
𝑃1 𝑚𝑜𝑙

 Put (a) and (b) in (4)

𝑐𝑚3 𝑐𝑚3 242.5 25200


30780 = 31023.6 ∗ (1 − + )
𝑚𝑜𝑙 𝑚𝑜𝑙 30780 307802
𝑐𝑚3 𝑐𝑚3
30780 = 31023.6 (1 − 0.007878 + 0.000026598)
𝑚𝑜𝑙 𝑚𝑜𝑙
𝑐𝑚3 𝑐𝑚3
30780 = 31023.6 ∗ 0.99215
𝑚𝑜𝑙 𝑚𝑜𝑙
𝑐𝑚3 𝑐𝑚 3
30780 = 30780
𝑚𝑜𝑙 𝑚𝑜𝑙
 Since

𝐿. 𝐻. 𝑆 = 𝑅. 𝐻. 𝑆
 Therefore

𝒄𝒎𝟑
𝑰𝒏𝒊𝒕𝒊𝒂𝒍 𝒗𝒐𝒍𝒖𝒎𝒆 = 𝑽𝟏 = 𝟑𝟎𝟕𝟖𝟎
𝒎𝒐𝒍

 Again using

𝑅𝑇 𝐵 𝐶
𝑉2 =
𝑃2
(1 + 𝑉 + 𝑉 2 ) → (5)
2 2

 Assume that
𝑐𝑚3
𝑉2 = 241.33 → (𝑐)
𝑚𝑜𝑙
𝑅𝑇 8.314 𝐽∗373.15 𝐾 𝑁∗𝑚 1.01325 𝑏𝑎𝑟∗𝑚2 1003 ∗𝑐𝑚3
𝑃2
= 𝑚𝑜𝑙∗𝐾∗55 𝑏𝑎𝑟
∗ 𝐽
∗ 101325 𝑁
∗ 1 𝑚3
𝑅𝑇 𝑐𝑚3
= 564.067 → (𝑑)
𝑃2 𝑚𝑜𝑙

 Put (c) and (d) in (4)

𝑐𝑚3 𝑐𝑚3 242.5 25200


241.33 = 564.067 ∗ (1 − + )
𝑚𝑜𝑙 𝑚𝑜𝑙 241.33 241.332
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𝑐𝑚3 𝑐𝑚3
241.33 = 564.067 (1 − 1.0048 + 0.4327)
𝑚𝑜𝑙 𝑚𝑜𝑙
𝑐𝑚3 𝑐𝑚3
241.33 = 564.067 ∗ 0.4278
𝑚𝑜𝑙 𝑚𝑜𝑙
3 3
𝑐𝑚 𝑐𝑚
241.33 = 241.33
𝑚𝑜𝑙 𝑚𝑜𝑙
 Since

𝐿. 𝐻. 𝑆 = 𝑅. 𝐻. 𝑆
 Therefore

𝒄𝒎𝟑
𝑭𝒊𝒏𝒂𝒍𝒗𝒐𝒍𝒖𝒎𝒆 = 𝑽𝟐 = 𝟐𝟒𝟏. 𝟑𝟑
𝒎𝒐𝒍

 Now from equation (3)

𝑉2
𝐵 𝐶 1
𝑊 = −𝑅𝑇 ∫ (1 + + ) 𝑑𝑉
𝑉1 𝑉 𝑉2 𝑉
𝑉2 𝑉2 𝑉2
1 1 1
𝑊 = −𝑅𝑇 [∫ 𝑑𝑉 + 𝐵 ∫ 2
𝑑𝑉 + 𝐶 ∫ 3
𝑑𝑉 ]
𝑉1 𝑉 𝑉1 𝑉 𝑉1 𝑉
𝑉 1 𝑉2 1 1 𝑉2
𝑊 = −𝑅𝑇 [|ln 𝑉|𝑉21− 𝐵 | | − 𝐶 | 2| ]
𝑉 𝑉1 2 𝑉 𝑉1
1 1 1 1 1
𝑊 = −𝑅𝑇 [(ln 𝑉2 − ln 𝑉1 ) − 𝐵 ( − ) − 𝐶 ( 2 − 2 )]
𝑉2 𝑉1 2 𝑉2 𝑉1
𝑉2 1 1 1 1 1
𝑊 = −𝑅𝑇 [ln − 𝐵 ( − ) − 𝐶 ( 2 − 2 )]
𝑉1 𝑉2 𝑉1 2 𝑉2 𝑉1
8.314 ∗ 𝐽 ∗ 373.15𝐾
𝑊 =−
𝑚𝑜𝑙 ∗ 𝐾
1 𝑘𝐽 241.33 1 1
∗ [ln + 242.5 ( − )
1000 𝐽 30780 241.33 30780
25200 1 1
− ( − )]
2 241.332 307802
𝑘𝐽
𝑊 = −3.102 [−4.848 + 0.996 − 0.2163]
𝑚𝑜𝑙
𝒌𝑱
𝑾 = 𝟏𝟐. 𝟔𝟐 Answer
𝒎𝒐𝒍

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(b)

𝑍 = 1 + 𝐵 ′ 𝑃 + 𝐶 ′ 𝑃2
𝑃𝑉
= 1 + 𝐵 ′ 𝑃 + 𝐶 ′ 𝑃2
𝑅𝑇
𝑅𝑇
𝑉= (1 + 𝐵′ 𝑃 + 𝐶 ′ 𝑃2 )
𝑃
1
𝑉 = 𝑅𝑇 ( + 𝐵′ + 𝐶′𝑃)
𝑃

 Differentiate w.r.t to pressure on both sides

𝑑𝑉 1
= 𝑅𝑇 (− 2 + 0 + 𝐶 ′ )
𝑑𝑃 𝑃
1
𝑑𝑉 = −𝑅𝑇 ( 2 + 𝐶′) 𝑑𝑃
𝑃

 Put in (2)

𝑃2
1
𝑊 = − ∫ −𝑃𝑅𝑇 ( 2
+ 𝐶 ′ ) 𝑑𝑃
𝑃1 𝑃
𝑃 1 𝑃
𝑊 = 𝑅𝑇 [∫𝑃 2 𝑑𝑃 + 𝐶′ ∫𝑃 2 𝑃𝑑𝑃 ]
1 𝑃 1

𝑃 𝐶′
𝑊 = 𝑅𝑇 [|𝑙𝑛𝑃|𝑃21 + |𝑃2 |𝑃𝑃21 ]
2

𝑃2
𝑊 = 𝑅𝑇 [ln + 𝐶 ′ (𝑃2 2 − 𝑃1 2 )]
𝑃1
8.314 ∗ 𝐽 ∗ 373.15𝐾 1 𝑘𝐽 55 3.492 ∗ 10−5 1
𝑊= ∗ [ln − 2
(552 − 1)𝑏𝑎𝑟 2 ]
𝑚𝑜𝑙 ∗ 𝐾 1000 𝐽 1 2 𝑏𝑎𝑟
3.102𝑘𝐽
𝑊= (3.9545)
𝑚𝑜𝑙
𝒌𝑱
𝑾 = 𝟏𝟐. 𝟐𝟔𝟖 Answer
𝒎𝒐𝒍

The answers for part (a) and (b) differ because the relations between the two sets of
parameters are exact only for infinite series

Problem 3.32:
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Calculate Z and V for ethylene at 25 oC and 12 bars by the following equations:


a) The truncated virial equation [Eq. (3.40)] with the following experimental values
of virial coefficients:
𝑩 = −𝟏𝟒𝟎 𝒄𝒎𝟑 𝒎𝒐𝒍−𝟏 𝑪 = 𝟕𝟐𝟎𝟎 𝒄𝒎𝟔 𝒎𝒐𝒍−𝟐
b) The truncated virial equation [Eq.(3.38)], with a value of B from the
generalized Pitzer correlations [Eq. (3.63)]
c) The Redlich/Kwong equation
d) The Soave/Redlich/Kwong equation
e) The Peng/Robinson equation.
Given Data:

𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇 = 25 ℃
𝑇 = (25 + 273.15)𝐾
𝑇 = 298.15 𝐾
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃 = 12 𝑏𝑎𝑟
Solution:
(a)

𝐵 = −140 𝑐𝑚3 𝑚𝑜𝑙 −1


𝐶 = 7200 𝑐𝑚6 𝑚𝑜𝑙 −2
 Given equation is

𝐵 𝐶
𝑍 =1+ +
𝑉 𝑉2

𝑃𝑉 𝐵 𝐶
=1+ +
𝑅𝑇 𝑉 𝑉2
𝑅𝑇 𝐵 𝐶
𝑉=(1 + + 2 ) → (1)
𝑃 𝑉 𝑉
𝑅𝑇 8.314 ∗ 𝐽 ∗ 298.15 𝐾 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 ∗ 𝑐𝑚3
= ∗ ∗ ∗
𝑃 𝑚𝑜𝑙 ∗ 𝐾 ∗ 12 ∗ 𝑏𝑎𝑟 𝐽 101325 𝑁 1 𝑚3
𝑅𝑇 𝑐𝑚3
= 2065.68
𝑉 𝑚𝑜𝑙

 Put in (1)

𝑐𝑚3 𝐵 𝐶
𝑉 = 2065.68 (1 + 𝑉 + 𝑉 2)
𝑚𝑜𝑙

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 Assume

𝑐𝑚3
𝑉 = 1919
𝑚𝑜𝑙

 Therefore

𝑐𝑚3 𝑐𝑚3 140 7200


1919 = 2065.68 (1 − + )
𝑚𝑜𝑙 𝑚𝑜𝑙 1919 19192
𝑐𝑚3 𝑐𝑚3
1919 = 2065.68 (0.9290)
𝑚𝑜𝑙 𝑚𝑜𝑙
𝑐𝑚3 𝑐𝑚3
1919 = 1919
𝑚𝑜𝑙 𝑚𝑜𝑙

 Since

𝐿. 𝐻. 𝑆 = 𝑅. 𝐻. 𝑆
 Therefore

𝒄𝒎𝟑
𝑽 = 𝟏𝟗𝟏𝟗 Answer
𝒎𝒐𝒍

 We know that

𝑃𝑉
𝑍=
𝑅𝑇
3
12 ∗ 𝑏𝑎𝑟 ∗ 1919 ∗ 𝑐𝑚 ∗ 𝑚𝑜𝑙 ∗ 𝐾 𝐽 101325 𝑁 1 𝑚3
𝑍= ∗ ∗ ∗
8.314 ∗ 𝐽 ∗ 298.15 ∗ 𝐾 ∗ 𝑚𝑜𝑙 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 𝑐𝑚3
𝒁 = 𝟎. 𝟗𝟐𝟗 Answer
(b)

 Given equation 3.38 is

𝐵𝑃
𝑍 =1+ → (2)
𝑅𝑇

 We know that

𝑇
𝑅𝑒𝑑𝑢𝑐𝑒𝑑 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇𝑟 =
𝑇𝑐
𝑇 = 𝑇𝑟 𝑇𝑐 → (𝑎)

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𝑃
𝑅𝑒𝑑𝑢𝑐𝑒𝑑 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃𝑟 =
𝑃𝑐
𝑃 = 𝑃𝑟 𝑃𝑐 → (𝑏)
 Put (a) and (b) in (2)

𝐵𝑃𝑟 𝑃𝑐
𝑍 =1+
𝑅𝑇𝑟 𝑇𝑐

 Since

𝐵𝑃
𝑅𝑒𝑑𝑢𝑐𝑒𝑑 𝑠𝑒𝑐𝑜𝑛𝑑 𝑣𝑖𝑟𝑖𝑎𝑙 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 = 𝐵̂ = 𝑐
𝑅𝑇𝑐

 Therefore
𝐵̂𝑃𝑟
𝑍 =1+ → (3)
𝑇𝑟
 Also

𝐵̂ = 𝐵𝑂 + 𝜔𝐵1
 Put in (3)

𝑃𝑟
𝑍 = 1 + (𝐵𝑂 + 𝜔𝐵1 ) → (4)
𝑇𝑟

 For ethylene (From Table B.1 Appendix B)

𝝎 = 𝟎. 𝟎𝟖𝟕 → (𝒊)
𝐶𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇𝑐 = 282.3 𝐾
𝑻 𝟐𝟗𝟖. 𝟏𝟓 𝑲
𝑻𝒓 = = = 𝟏. 𝟎𝟓𝟔 → (𝒊𝒊)
𝑻𝒄 𝟐𝟖𝟐. 𝟑 𝑲
𝐶𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃𝑐 = 50.40 𝑏𝑎𝑟
𝑷 𝟏𝟐 𝐛𝐚𝐫
𝑷𝒓 = = = 𝟎. 𝟐𝟑𝟖 → (𝒊𝒊𝒊)
𝑷𝒄 𝟓𝟎.𝟒𝟎 𝐛𝐚𝐫

 Also we have

0.422
𝐵𝑜 = 0.083 −
𝑇𝑟 1.6
0.422
𝐵𝑜 = 0.083 −
1.0561.6
𝑩𝒐 = −𝟎. 𝟑𝟎𝟒 → (𝒊𝒗)

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0.172
𝐵1 = 0.139 −
1.0564.2
𝑩 = 𝟐. 𝟏𝟖𝟑 ∗ 𝟏𝟎−𝟑 → (𝒗)
𝟏

 Put (i), (ii), (iii), (iv) & (v) in (4)

0.238
𝑍 = 1 + (−0.304 + 0.087 ∗ 2.183 ∗ 10−3 )
1.056
𝒁 = 𝟎. 𝟗𝟑𝟏 Answer
 We know that

𝑃𝑉
𝑍=
𝑅𝑇
𝑍𝑅𝑇
𝑉=
𝑃
0.931 ∗ 8.314 𝐽 ∗ 298.15 𝐾 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 𝑐𝑚3
𝑉= ∗ ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 12 𝑏𝑎𝑟 𝐽 101325 𝑁 1 𝑚3
𝒄𝒎𝟑
𝑽 = 𝟏𝟗𝟐𝟑. Answer
𝒎𝒐𝒍

(c)

 The Redlich/Kwong equation is

𝑍−𝛽
𝑍 = 1 + 𝛽 − 𝑞𝛽 (𝑍+𝜖𝛽)(𝑍+𝜎𝛽) → (5)

 Where

𝑃𝑟
𝛽=𝛺
𝑇𝑟
 From table 3.1

𝟏
𝝈 = 𝟏, 𝛀 = 𝟎. 𝟎𝟖𝟔𝟔𝟒, 𝜺 = 𝟎, 𝝍 = 𝟎. 𝟒𝟐𝟕𝟒𝟖, 𝜶(𝑻𝒓 ) = 𝑻𝒓 −𝟐
 Now

0.238
𝛽 = 0.08664 ∗
1.056
𝜷 = 𝟎. 𝟎𝟏𝟗𝟓 → (𝒊′ )

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 Also

𝜓𝛼(𝑇𝑟 )
𝑞=
Ω𝑇𝑟
1
0.42748 ∗ 1.056−2
𝑞=
0.08664 ∗ 1.056
𝒒 = 𝟒. 𝟓𝟒𝟕 → (𝒊𝒊′ )
 Put (i’) and (ii’) in (5)

𝑍−𝛽
𝑍 = 1 + 0.0195 − 4.547 ∗ 0.0195 (𝑍+𝜖𝛽)(𝑍+𝜎𝛽)

 Assume

𝒁 = 𝟎. 𝟗𝟐𝟖
0.928 − 0.0195
0.928 = 1.0195 − 0.08866
0.928(0.928 + 0.0195)
0.928 = 1.0195 − 0.08866 ∗ 1.033
0.928 = 0.928
 Since

𝑳. 𝑯. 𝑺 = 𝑹. 𝑯. 𝑺
 Therefore,

𝒁 = 𝟎. 𝟗𝟐𝟖 Answer

 We know that

𝑃𝑉
𝑍=
𝑅𝑇
𝑍𝑅𝑇
𝑉=
𝑃
0.928 ∗ 8.314 𝐽 ∗ 298.15 𝐾 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 𝑐𝑚3
𝑉= ∗ ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 12 𝑏𝑎𝑟 𝐽 101325 𝑁 1 𝑚3
𝒄𝒎𝟑
𝑽 = 𝟏𝟗𝟏𝟔. 𝟖 Answer
𝒎𝒐𝒍

(d)

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 From table 3.1

𝝈 = 𝟏, 𝛀 = 𝟎. 𝟎𝟖𝟔𝟔𝟒, 𝜺 = 𝟎, 𝝍 = 𝟎. 𝟒𝟐𝟕𝟒𝟖, 𝜶(𝑻𝒓 ) = 𝜶𝑺𝑹𝑲 (𝑻𝒓 ; 𝝎)

1 2
2)
𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [1 + {(0.480 + 1.574𝜔 − 0.176𝜔 (1 − 𝑇𝑟 )}]
2

1 2
2
𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [1 + {(0.480 + 1.574 ∗ 0.087 − 0.176 ∗ 0.087 ) (1 − 1.0562 )}]

𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [0.9828]2



𝜶𝑺𝑹𝑲 (𝑻𝒓 ; 𝝎) = 𝟎. 𝟗𝟔𝟔 → (𝒊𝒊𝒊 )

 Now

𝜓𝛼(𝑇𝑟 )
𝑞=
Ω𝑇𝑟
0.42748 ∗ 0.966
𝑞=
0.08664 ∗ 1.056
𝒒 = 𝟒. 𝟓𝟏𝟓 → (𝒊𝒊𝒊′ )
 Put (i’) and (iii’) in (5)

𝑍−𝛽
𝑍 = 1 + 0.0195 − 4.515 ∗ 0.0195 (𝑍+𝜖𝛽)(𝑍+𝜎𝛽)

 Assume

𝒁 = 𝟎. 𝟗𝟐𝟖
0.928 − 0.0195
0.928 = 1.0195 − 0.08803
0.9(0.9 + 0.0195)
0.928 = 1.0195 − 0.2383 ∗ 1.36
0.928 = 0.928
 Since

𝑳. 𝑯. 𝑺 = 𝑹. 𝑯. 𝑺
 Therefore,

𝒁 = 𝟎. 𝟗𝟐𝟖 Answer

 We know that
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𝑃𝑉
𝑍=
𝑅𝑇
𝑍𝑅𝑇
𝑉=
𝑃
0.928 ∗ 8.314 𝐽 ∗ 298.15 𝐾 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 𝑐𝑚3
𝑉= ∗ ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 12 𝑏𝑎𝑟 𝐽 101325 𝑁 1 𝑚3
𝒄𝒎𝟑
𝑽 = 𝟏𝟗𝟏𝟕 Answer
𝒎𝒐𝒍

(e)

 From table 3.1

𝝈 = 𝟏 + √𝟐 = 𝟐. 𝟒𝟏, 𝛀 = 𝟎. 𝟎𝟕𝟕𝟖𝟎, 𝜺 = 𝟏 − √𝟐 = −𝟎. 𝟒𝟏𝟒, 𝝍 = 𝟎. 𝟒𝟓𝟕𝟐𝟒,


𝜶(𝑻𝒓 ) = 𝜶𝑺𝑹𝑲 (𝑻𝒓 ; 𝝎)
 Now
𝑃𝑟
𝛽=𝛺
𝑇𝑟
0.238
𝛽 = 0.07780 ∗
1.056
𝜷 = 𝟎. 𝟎𝟏𝟕𝟓 → (𝒊𝒗′ )
1 2
𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [1 + {(0.37464 + 1.54226𝜔 − 0.26992𝜔2 ) (1 − 𝑇𝑟 2 )}]
1 2
2
𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [1 + {(0.37464 + 1.54226 ∗ 0.087 − 0.26992 ∗ 0.087 ) (1 − 1.0562 )}]

𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [0.986]2


𝜶𝑺𝑹𝑲 (𝑻𝒓 ; 𝝎) = 𝟎. 𝟗𝟕𝟐𝟐

 Now

𝜓𝛼(𝑇𝑟 )
𝑞=
Ω𝑇𝑟
0.42748 ∗ 0.9722
𝑞=
0.08664 ∗ 1.056
𝒒 = 𝟒. 𝟓𝟒𝟐 → (𝒗′)

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 Put (iv’) and (v’) in (5)

𝑍−𝛽
𝑍 = 1 + 0.0175 − 4.542 ∗ 0.0175 (𝑍+𝜖𝛽)(𝑍+𝜎𝛽)

 Assume

𝒁 = 𝟎. 𝟗𝟐
0.92 − 0.0175
0.92 = 1.0175 − 0.07949
(0.92 − 0.414 ∗ 0.0175)(0.92 + 2.41 ∗ 0.0175)
0.92 = 1.0175 − 0.07949 ∗ 1.027
0.92 ≈ 0.93
 Since

𝑳. 𝑯. 𝑺 ≈ 𝑹. 𝑯. 𝑺
 Therefore,

𝒁 = 𝟎. 𝟗𝟐 Answer

 We know that

𝑃𝑉
𝑍=
𝑅𝑇
𝑍𝑅𝑇
𝑉=
𝑃
0.92 ∗ 8.314 𝐽 ∗ 298.15 𝐾 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 𝑐𝑚3
𝑉= ∗ ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 12 𝑏𝑎𝑟 𝐽 101325 𝑁 1 𝑚3
𝒄𝒎𝟑
𝑽 = 𝟏𝟗𝟎𝟎. 𝟒 Answer
𝒎𝒐𝒍

Problem 3.33:

Calculate Z and V for ethane at 50 oC and 15 bars by the following equations:


a) The truncated virial equation [Eq. (3.40)] with the following experimental
values of virial coefficients:
𝑩 = −𝟏𝟓𝟔. 𝟕 𝒄𝒎𝟑 𝒎𝒐𝒍−𝟏 𝑪 = 𝟗𝟔𝟓𝟎 𝒄𝒎𝟔 𝒎𝒐𝒍−𝟐
b) The truncated virial equation [Eq.(3.38)], with a value of B from the
generalized Pitzer correlations [Eq. (3.63)]
c) The Redlich/Kwong equation
d) The Soave/Redlich/Kwong equation
e) The Peng/Robinson equation.
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Given Data:

𝑇𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇 = 50℃
𝑇 = (50 + 273.15)𝐾
𝑇 = 323.15 𝐾
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃 = 15 𝑏𝑎𝑟
Solution:
(a)

𝐵 = −156.7 𝑐𝑚3 𝑚𝑜𝑙 −1


𝐶 = 9650 𝑐𝑚6 𝑚𝑜𝑙 −2
 Given equation is

𝐵 𝐶
𝑍 =1+ +
𝑉 𝑉2
𝑃𝑉 𝐵 𝐶
=1+ + 2
𝑅𝑇 𝑉 𝑉
𝑅𝑇 𝐵 𝐶
𝑉= (1 + + 2 ) → (1)
𝑃 𝑉 𝑉

𝑅𝑇 8.314 ∗ 𝐽 ∗ 323.15 𝐾 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 ∗ 𝑐𝑚3


= ∗ ∗ ∗
𝑃 𝑚𝑜𝑙 ∗ 𝐾 ∗ 15 ∗ 𝑏𝑎𝑟 𝐽 101325 ∗ 𝑁 1 𝑚3
𝑅𝑇 𝑐𝑚3
= 2065.68
𝑉 𝑚𝑜𝑙

 Put in (1)

𝑐𝑚3 𝐵 𝐶
𝑉 = 1791 (1 + 𝑉 + 𝑉 2)
𝑚𝑜𝑙

 Assume

𝑐𝑚3
𝑉 = 1625
𝑚𝑜𝑙

 Therefore

𝑐𝑚3 𝑐𝑚3 156.7 9650


1625 = 1791 (1 − + )
𝑚𝑜𝑙 𝑚𝑜𝑙 1625 16252
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𝑐𝑚3 𝑐𝑚3
1625 = 1791 (0.9072)
𝑚𝑜𝑙 𝑚𝑜𝑙
𝑐𝑚3 𝑐𝑚3
1625 = 1625
𝑚𝑜𝑙 𝑚𝑜𝑙

 Since

𝐿. 𝐻. 𝑆 = 𝑅. 𝐻. 𝑆
 Therefore

𝒄𝒎𝟑
𝑽 = 𝟏𝟔𝟐𝟓 Answer
𝒎𝒐𝒍

 We know that

𝑃𝑉
𝑍=
𝑅𝑇
3
15 ∗ 𝑏𝑎𝑟 ∗ 1625 ∗ 𝑐𝑚 ∗ 𝑚𝑜𝑙 ∗ 𝐾 𝐽 101325 𝑁 1 𝑚3
𝑍= ∗ ∗ ∗
8.314 ∗ 𝐽 ∗ 323.15 ∗ 𝐾 ∗ 𝑚𝑜𝑙 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 𝑐𝑚3
𝒁 = 𝟎. 𝟗𝟎𝟕 Answer
(b)

 Given equation 3.38 is

𝐵𝑃
𝑍 =1+ → (2)
𝑅𝑇

 We know that

𝑇
𝑅𝑒𝑑𝑢𝑐𝑒𝑑 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇𝑟 =
𝑇𝑐
𝑇 = 𝑇𝑟 𝑇𝑐 → (𝑎)
𝑃
𝑅𝑒𝑑𝑢𝑐𝑒𝑑 𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃𝑟 =
𝑃𝑐
𝑃 = 𝑃𝑟 𝑃𝑐 → (𝑏)
 Put (a) and (b) in (2)

𝐵𝑃𝑟 𝑃𝑐
𝑍 =1+
𝑅𝑇𝑟 𝑇𝑐

 Since

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𝐵𝑃
𝑅𝑒𝑑𝑢𝑐𝑒𝑑 𝑠𝑒𝑐𝑜𝑛𝑑 𝑣𝑖𝑟𝑖𝑎𝑙 𝑐𝑜𝑒𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑡 = 𝐵̂ = 𝑐
𝑅𝑇𝑐

 Therefore
𝐵̂𝑃𝑟
𝑍 =1+ → (3)
𝑇𝑟
 Also

𝐵̂ = 𝐵𝑂 + 𝜔𝐵1
 Put in (3)

𝑃𝑟
𝑍 = 1 + (𝐵𝑂 + 𝜔𝐵1 ) → (4)
𝑇𝑟

 For ethylene (From Table B.1 Appendix B)

𝝎 = 𝟎. 𝟏 → (𝒊)
𝐶𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑡𝑒𝑚𝑝𝑒𝑟𝑎𝑡𝑢𝑟𝑒 = 𝑇𝑐 = 305.3 𝐾
𝑻 𝟑𝟐𝟑. 𝟏𝟓 𝑲
𝑻𝒓 = = = 𝟏. 𝟎𝟓𝟖 → (𝒊𝒊)
𝑻𝒄 𝟑𝟎𝟓. 𝟑 𝑲
𝐶𝑟𝑖𝑡𝑖𝑐𝑎𝑙 𝑝𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = 𝑃𝑐 = 48.72 𝑏𝑎𝑟
𝑷 𝟏𝟓 𝐛𝐚𝐫
𝑷𝒓 = = = 𝟎. 𝟑𝟎𝟖 → (𝒊𝒊𝒊)
𝑷𝒄 𝟒𝟖.𝟕𝟐 𝐛𝐚𝐫

 Also we have

0.422
𝐵𝑜 = 0.083 −
𝑇𝑟 1.6
0.422
𝐵𝑜 = 0.083 −
1.0581.6
𝑩𝒐 = −𝟎. 𝟑𝟎𝟑 → (𝒊𝒗)
0.172
𝐵1 = 0.139 −
1.0584.2
𝑩𝟏 = 𝟑. 𝟐𝟔𝟔 ∗ 𝟏𝟎−𝟑 → (𝒗)
 Put (i), (ii), (iii), (iv) & (v) in (4)

0.308
𝑍 = 1 + (−0.303 + 0.1 ∗ 3.266 ∗ 10−3 )
1.058
𝒁 = 𝟎. 𝟗𝟏𝟐 Answer

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 We know that

𝑃𝑉
𝑍=
𝑅𝑇
𝑍𝑅𝑇
𝑉=
𝑃
0.912 ∗ 8.314 𝐽 ∗ 323.15 𝐾 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 𝑐𝑚3
𝑉= ∗ ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 15 𝑏𝑎𝑟 𝐽 101325 𝑁 1 𝑚3
𝒄𝒎𝟑
𝑽 = 𝟏𝟔𝟑𝟑. 𝟑𝟔 Answer
𝒎𝒐𝒍

(c)

 The Redlich/Kwong equation is

𝑍−𝛽
𝑍 = 1 + 𝛽 − 𝑞𝛽 (𝑍+𝜖𝛽)(𝑍+𝜎𝛽) → (5)

 Where

𝑃𝑟
𝛽=𝛺
𝑇𝑟
 From table 3.1

𝟏
𝝈 = 𝟏, 𝛀 = 𝟎. 𝟎𝟖𝟔𝟔𝟒, 𝜺 = 𝟎, 𝝍 = 𝟎. 𝟒𝟐𝟕𝟒𝟖, 𝜶(𝑻𝒓 ) = 𝑻𝒓 −𝟐
 Now

0.308
𝛽 = 0.08664 ∗
1.058
𝜷 = 𝟎. 𝟎𝟐𝟓𝟐 → (𝒊′ )
 Also

𝜓𝛼(𝑇𝑟 )
𝑞=
Ω𝑇𝑟
1
0.42748 ∗ 1.058−2
𝑞=
0.08664 ∗ 1.058
𝒒 = 𝟒. 𝟓𝟑𝟑 → (𝒊𝒊′ )
 Put (i’) and (ii’) in (5)

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𝑍−𝛽
𝑍 = 1 + 0.0252 − 4.533 ∗ 0.0252 (𝑍+𝜖𝛽)(𝑍+𝜎𝛽)

 Assume

𝒁 = 𝟎. 𝟗𝟎𝟔
0.906 − 0.0252
0.906 = 1.0252 − 0.114
0.906(0.906 + 0.0252)
0.906 = 1.0252 − 0.114 ∗ 1.044
0.906 = 0.906
 Since

𝑳. 𝑯. 𝑺 = 𝑹. 𝑯. 𝑺
 Therefore,

𝒁 = 𝟎. 𝟗𝟎𝟔 Answer

 We know that

𝑃𝑉
𝑍=
𝑅𝑇
𝑍𝑅𝑇
𝑉=
𝑃
0.906 ∗ 8.314 𝐽 ∗ 323.15 𝐾 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 𝑐𝑚3
𝑉= ∗ ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 15 𝑏𝑎𝑟 𝐽 101325 𝑁 1 𝑚3
𝒄𝒎𝟑
𝑽 = 𝟏𝟔𝟐𝟐. 𝟕 Answer
𝒎𝒐𝒍

(d)

 From table 3.1

𝝈 = 𝟏, 𝛀 = 𝟎. 𝟎𝟖𝟔𝟔𝟒, 𝜺 = 𝟎, 𝝍 = 𝟎. 𝟒𝟐𝟕𝟒𝟖, 𝜶(𝑻𝒓 ) = 𝜶𝑺𝑹𝑲 (𝑻𝒓 ; 𝝎)

1 2
𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [1 + {0.480 + 1.574𝜔 − 0.176𝜔2 (1 − 𝑇𝑟 2 )}]
1 2
2
𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [1 + {0.480 + 1.574 ∗ 0.1 − 0.176 ∗ 0.1 (1 − 1.0582 )}]

𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [1 + 0.6374]2


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𝜶𝑺𝑹𝑲 (𝑻𝒓 ; 𝝎) = 𝟐. 𝟔𝟖𝟏 → (𝒊𝒊𝒊 )

 Now

𝜓𝛼(𝑇𝑟 )
𝑞=
Ω𝑇𝑟
0.42748 ∗ 2.681
𝑞=
0.08664 ∗ 1.058
𝒒 = 𝟏𝟐. 𝟓𝟎 → (𝒊𝒊𝒊′ )
 Put (i’) and (iii’) in (5)

𝑍−𝛽
𝑍 = 1 + 0.0252 − 12.50 ∗ 0.0252 (𝑍+𝜖𝛽)(𝑍+𝜎𝛽)

 Assume

𝒁 = 𝟎. 𝟗𝟎𝟕
0.907 − 0.0252
0.907 = 1.0252 − 0.315
0.907(0.907 + 0.0252)
0.907 = 1.0252 − 0.315 ∗ 1.0429
0.695 = 0.695
 Since

𝑳. 𝑯. 𝑺 = 𝑹. 𝑯. 𝑺
 Therefore,

𝒁 = 𝟎. 𝟔𝟗𝟓 Answer

 We know that

𝑃𝑉
𝑍=
𝑅𝑇
𝑍𝑅𝑇
𝑉=
𝑃
0.695 ∗ 8.314 𝐽 ∗ 298.15 𝐾 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 𝑐𝑚3
𝑉= ∗ ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 12 𝑏𝑎𝑟 𝐽 101325 𝑁 1 𝑚3
𝒄𝒎𝟑
𝑽 = 𝟏𝟒𝟑𝟓. 𝟔 Answer
𝒎𝒐𝒍

(e)

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 From table 3.1

𝝈 = 𝟏, 𝛀 = 𝟎. 𝟎𝟕𝟕𝟖𝟎, 𝜺 = 𝟎, 𝝍 = 𝟎. 𝟒𝟓𝟕𝟐𝟒, 𝜶(𝑻𝒓 ) = 𝜶𝑺𝑹𝑲 (𝑻𝒓 ; 𝝎)


 Now
𝑃𝑟
𝛽=𝛺
𝑇𝑟
0.238
𝛽 = 0.07780 ∗
1.056
𝜷 = 𝟎. 𝟎𝟏𝟕𝟓 → (𝒊𝒗′ )
1 2
2
𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [1 + {0.37464 + 1.54226𝜔 − 0.26992𝜔 (1 − 𝑇𝑟 )}]
2

𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [1
2 2
+ {0.37464 + 1.54226 ∗ 0.087 − 0.26992 ∗ 0.0872 (1 − 1.056 )}]

𝛼𝑆𝑅𝐾 (𝑇𝑟 ; 𝜔) = [1 + 0.509]2


𝜶𝑺𝑹𝑲 (𝑻𝒓 ; 𝝎) = 𝟐. 𝟐𝟕𝟕

 Now

𝜓𝛼(𝑇𝑟 )
𝑞=
Ω𝑇𝑟
0.42748 ∗ 2.277
𝑞=
0.08664 ∗ 1.056
𝒒 = 𝟏𝟎. 𝟔𝟒 → (𝒗′)
 Put (iv’) and (v’) in (5)

𝑍−𝛽
𝑍 = 1 + 0.0175 − 10.64 ∗ 0.0175 (𝑍+𝜖𝛽)(𝑍+𝜎𝛽)

 Assume

𝒁 = 𝟎. 𝟕𝟗𝟑
0.793 − 0.0175
0.793 = 1.0175 − 0.1862
0.793(0.793 + 0.0175)
0.793 = 1.0175 − 0.1862 ∗ 1.2066

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0.793 = 0.793
 Since

𝑳. 𝑯. 𝑺 = 𝑹. 𝑯. 𝑺
 Therefore,

𝒁 = 𝟎. 𝟕𝟗𝟑 Answer

 We know that

𝑃𝑉
𝑍=
𝑅𝑇
𝑍𝑅𝑇
𝑉=
𝑃
0.793 ∗ 8.314 𝐽 ∗ 298.15 𝐾 𝑁 ∗ 𝑚 1.01325 𝑏𝑎𝑟 ∗ 𝑚2 1003 𝑐𝑚3
𝑉= ∗ ∗ ∗
𝑚𝑜𝑙 ∗ 𝐾 ∗ 12 𝑏𝑎𝑟 𝐽 101325 𝑁 1 𝑚3
𝒄𝒎𝟑
𝑽 = 𝟏𝟔𝟑𝟖. 𝟏 Answer
𝒎𝒐𝒍

99