Nama : Winda Chairunissa

NPM : 1415041066

Mata Kuliah : Termodinamika 1

Tugas 4

Example 3.7 (page 84, 4th edition)

Given that the vapor pressure of methyl chloride at 60⁰C is 13,76 bar use the

Redlich/Kwong equation and Van der Waals equation to calculate the molar volumes of

saturated vapor and saturated liquid at these conditions. Compare them! (R = 83,14

bar/mol.K)

Solution

First we evaluate the constants a and b by Eqs. (3.40) and (3.41) with the value of Tc

and Pc taken from Appendix.B page 572 where Tc and Pc for methyl chloride is 416,3

K and 66,8 bar, so it will given :

0.42748𝑅2 𝑇𝑐 2.5
𝑎=
𝑃𝑐

(0.42748)(83.14)2 (416.3)2.5
𝑎=
66,8

(0,42748)(6912,26)(3536030,70)
𝑎=
66,8

10448450592,4
𝑎=
66,8

𝑐𝑚6 𝑏𝑎𝑟√𝐾
𝑎 = 156413922
𝑚𝑜𝑙

Or we can simplify it became

𝑐𝑚6 𝑏𝑎𝑟√𝐾
8
𝑎 = 1,564 × 10
𝑚𝑜𝑙

And we can evaluate value of b is

0,08664𝑅𝑇𝑐
𝑏=
𝑃𝑐
 (0,08664)(83,14)(416,3)
𝑏=
(66,8)

2998,713
𝑏=
66,8

𝑏 = 44,891 𝑐𝑚3 /𝑚𝑜𝑙

For evaluation of the molar volume of saturated vapor, we substitute known values into

Equation (3.37) ; this gives

𝑅𝑇 𝑎(𝑉𝑖 − 𝑏)
𝑉𝑖+1 = + 𝑏 − 1/2
𝑃 𝑇 𝑃𝑉𝑖 (𝑉𝑖 + 𝑏)

Before we complete the equation above, we have to find the value of 𝑉𝑖 = 𝑉0 , where
𝑅𝑇
equation of 𝑉0 for ideal gas is 𝑉0 = 𝑃
. Hence we use T = 60⁰C or 333 K and P = 13,76

bar. So the value of 𝑉0 is

𝑅𝑇
𝑉0 =
𝑃

(83,14)(333)
𝑉0 =
(13,76)

27685,62
𝑉0 =
13,76

𝑉0 = 2012,036 𝑐𝑚3 /𝑚𝑜𝑙

We have known that 𝑉𝑖 = 𝑉0 , so we can complete 𝑉𝑖+1 with T = 60⁰C or 333 K and P =

13.76 bar, so

𝑅𝑇 𝑎(𝑉𝑖 − 𝑏)
𝑉𝑖+1 = + 𝑏 − 1/2
𝑃 𝑇 𝑃𝑉𝑖 (𝑉𝑖 + 𝑏)

156,414 × 106 (2012,036 − 44,891)

𝑉𝑖+1 = 2012,036 + 44.891 −
(333)1/2 (13.76)(2012,036)(2012,036 + 44,891)

(156,414 × 106 )(1967.145)

𝑉𝑖+1 = 2056,927 −
(18,248)(27685,615)(2056,927)

307,689 × 109
𝑉𝑖+1 = 2056,927 −
103,917 × 107

307,689 × 109
𝑉𝑖+1 = 2056,927 −
103,917 × 107

𝑉𝑖+1 = 2056,927 − 5,078

 𝑉𝑖+1 = 2051,849 𝑐𝑚3 /𝑚𝑜𝑙

For evaluation of the molar volume of saturated liquid, we substitute known values into

equation (3.38) and (3.39),

1 𝑅𝑇 2 𝑎𝑏
𝑉𝑖+1 = (𝑉𝑖3 − 𝑉𝑖 − 1/2 )
𝑐 𝑃 𝑃𝑇

𝑏𝑅𝑇 𝑎
𝑐 = 𝑏2 + − 1/2
𝑃 𝑃𝑇

Iteration starts with 𝑉𝑖 = 𝑉0 = 𝑏 = 44,891 𝑐𝑚3 /𝑚𝑜𝑙, and before we complete equation

above, first we have to find c value, where

𝑏𝑅𝑇 𝑎
𝑐 = 𝑏2 + − 1/2
𝑃 𝑃𝑇

(44,891)(83,14)(333) 156,414 × 106

𝑐 = (44,891)2 + −
(13,76) (13,76)(333)1/2

1,243 × 106 156,414 × 106

𝑐 = (44,891)2 + −
13,76 251,096

𝑐 = 2,015 × 103 + 9,033 × 104 − 6,229 × 105

𝑐 = −1,581 × 1010

After that, we can finish 𝑉𝑖+1 in saturated liquid by equation , (3.38) with 𝑉𝑖 = 𝑉0 = 𝑏 =

44,891 𝑐𝑚3 /𝑚𝑜𝑙, so 𝑉𝑖+1 is

1 𝑅𝑇 2 𝑎𝑏
𝑉𝑖+1 = (𝑉𝑖3 − 𝑉𝑖 − 1/2 )
𝑐 𝑃 𝑃𝑇

1 3 3
(156,414 × 106 )(44,891)
𝑉𝑖+1 = ((44,891) − (2012,036)(2,015 × 10 ) − )
−207,338 × 106 251,096

1
𝑉𝑖+1 = (9,101 × 105 − 4,054 × 106 − 2,796 × 107 )
−207,338 × 106

𝑉𝑖+1 = −4,823 × 10−3 (−3.11254 × 107 )

𝑉𝑖+1 = 34,34 𝑐𝑚3 /𝑚𝑜𝑙

Use Microsoft Excel to complete iteration till the volume of saturated vapor and liquid

vapor methyl chloride is constant. Then it results can we see in the table below
 Table 1. Redlich Kwong Equation

Iteration in Saturated Vapor Iteration in Saturated Liquid

V0 2012,036 V0 44,891

V1 2012,036 V1 44,891

V1 + 1 2051,849 V1 + 1 34,3407

V1 + 2 2051,9433 V1 + 2 34,3406

V1 + 3 2051,9435 V1 + 3 34,3406

V1 + 4 2051,9435 V1 + 4 34,3406

Now we finish volume iteration of saturated vapor and liquid vapor methyl chloride by

Van der Waals equation, it given us for a and b in equation below

27𝑅2 𝑇𝑐 2
𝑎=
64𝑃𝑐

𝑅𝑇𝑐
𝑏=
8𝑃𝑐

With value of Tc and Pc is same like value who we use in Redlich Kwong equation that

we can found in Appebdix.B page 527 for methyl chloride.

27𝑅2 𝑇𝑐 2
𝑎=
64𝑃𝑐

27(83.14)2 (416.3)2
𝑎=
64(66.8)

𝑎 = 7,565 × 106

And then for b,

𝑅𝑇𝑐
𝑏=
8𝑃𝑐

(83,14)(416,3)
𝑏=
8(66,8)

𝑏 = 64,766
To iteration the volume we following Van Der Waals cubic iteration will be written

below for saturated vapor volume and for saturated liquid, where 𝑉0 = 2012,036 𝑐𝑚3 /

𝑚𝑜𝑙, the volume iteration given 𝑉𝑖+1 as follows

𝑅𝑇 𝑎 𝑎𝑏
𝑓(𝑉𝑛) = 𝑉𝑛3 − (𝑏 + ) 𝑉𝑛2 + × 𝑉𝑛 −
𝑃 𝑃 𝑃

𝑅𝑇 𝑎
𝑓′(𝑉𝑛) = 3𝑉𝑛3 − 2 (𝑏 + ) 𝑉𝑛 +
𝑃 𝑃

𝑓(𝑉𝑖)
𝑉𝑖+1 = 𝑉𝑖 −
𝑓′(𝑉𝑖)

Finally we can solve 𝑉𝑖+1 for volume iteration,

𝑅𝑇 𝑎 𝑎𝑏
𝑓(𝑉𝑜) = 𝑉𝑜 3 − (𝑏 + ) 𝑉𝑜 2 + × 𝑉𝑜 −
𝑃 𝑃 𝑝

𝑓(𝑉𝑜) = 808457633,1

𝑅𝑇 𝑎
𝑓′(𝑉𝑜) = 3𝑉𝑜3 − 2 (𝑏 + ) 𝑉𝑜 +
𝑃 𝑃

𝑓′(𝑉𝑜) = 24428113708

𝑓(𝑉𝑜)
𝑉𝑖 = 𝑉𝑜 −
𝑓′(𝑉𝑜)

𝑉𝑖 = 2012,003242

Use Microsoft Excel to complete iteration till the volume of saturated vapor and liquid

vapor methyl chloride is constant. Then it results can we see in the table below

Table 2. Van der Waals Equation

fo 808457633,1 f'o 24428113708 V1 2012,003242

f1 808314086,7 f'1 24426908049 V2 2011,970151

f2 808170567,3 f'2 24425702583 V3 2011,937064

f3 808027075,1 f'3 24424497311 V4 2011,903981

f4 807883609,8 f'4 24423292234 V5 2011,870903

f5 807740171,7 f'5 24422087351 V6 2011,837829

f6 807596760,6 f'6 24420882662 V7 2011,804759

f7 807453376,5 f'7 24419678167 V8 2011,771693

f8 807310019,5 f'8 24418473866 V9 2011,738632

f9 807166689,5 f'9 24417269759 V10 2011,705574

f10 807023386,6 f'10 24416065846 V11 2011,672521

f11 806880110,6 f'11 24414862127 V12 2011,639473

f12 806736861,7 f'12 24413658602 V13 2011,606428

f13 806593639,9 f'13 24412455271 V14 2011,573388

f14 806450445 f'14 24411252133 V15 2011,540352

f15 806307277,1 f'15 24410049190 V16 2011,50732