FQ1-2016.

2 Ejemplo 02
Determine el trabajo molar, el trabajo absoluto, el trabajo específico y la dilatación térmica promedio para
un proceso isobárico a 30atm, donde 30mol de metano gaseoso (𝑀 = 16.04276g/mol, 𝑇𝑐 = 190.55K, 𝑃𝑐 =
4604208Pa) se calientan desde 15°C hasta 50°C, si el metano cumple: (a) la ecuación del gas ideal, (b) la
ecuación de Van der Waals, (c) la ecuación de Redlich-Kwong, (d) la ecuación del primer virial (con
𝐵(15℃) = −0.000045912715m3 /mol y 𝐵(50℃) = −0.000033309842m3 /mol ), y (d) la ecuación de Soave-
Redlich-Kwong.

RAZONAMIENTO PREVIO:
Por definición el trabajo de expansión esta dado por:
𝑑𝑊 = −𝑃 · 𝑑𝑉
Y el diferencial de volumen esta dado por:
𝜕𝑉 𝜕𝑉 𝜕𝑉
𝑑𝑉 = ( ) 𝑑𝑇 + ( ) 𝑑𝑃 + ( ) 𝑑𝑛
𝜕𝑇 𝑃,𝑛 𝜕𝑃 𝑇,𝑛 𝜕𝑛 𝑇,𝑃
Sustituyendo:
𝜕𝑉 𝜕𝑉 𝜕𝑉
𝑑𝑊 = −𝑃 · [( ) 𝑑𝑇 + ( ) 𝑑𝑃 + ( ) 𝑑𝑛]
𝜕𝑇 𝑃,𝑛 𝜕𝑃 𝑇,𝑛 𝜕𝑛 𝑇,𝑃
Para un sistema cerrado (𝑑𝑛 = 0) a presión constante (𝑑𝑃 = 0):
𝜕𝑉
𝑑𝑊 = −𝑃 · ( ) 𝑑𝑇
𝜕𝑇 𝑃,𝑛
Aplicando la definición de la dilatación isobárica:
1 𝜕𝑉
𝛼= ( )
𝑉 𝜕𝑇
Entonces:
𝑑𝑊 = −𝑃 · 𝑉 · 𝛼 · 𝑑𝑇
1 𝑑𝑊 1 𝑊
𝛼=− · ≈− ·
𝑃 · 𝑉 𝑑𝑇 𝑃 · 𝑉0 ∆𝑇

RESOLUCIÓN:

(a) Gas ideal

𝜕𝑉𝑚
𝑑𝑊𝑚 = −𝑃 · ( ) 𝑑𝑇
𝜕𝑇 𝑃
𝑅·𝑇
𝑉𝑚 =
𝑃
𝜕𝑉𝑚 𝑅
( ) =
𝜕𝑇 𝑃 𝑃
𝑇1 𝑇1
𝑅
𝑊𝑚 = −𝑃 · ∫ · 𝑑𝑇 = −𝑅 ∫ 𝑑𝑇 = −𝑅 · (𝑇1 − 𝑇0 ) =
𝑇0 𝑃 𝑇0
𝑊𝑚 = −8.314J/(mol · K) · (50 − 15)K = −𝟐𝟗𝟎. 𝟗𝟗𝐉/𝐦𝐨𝐥

𝑊 = 𝑛 · 𝑊𝑚 = 30mol · (−290.99J/mol) = −𝟖𝟕𝟐𝟗. 𝟕𝐉

𝑊 𝑊 𝑊𝑚 −290.99J/mol
𝑤= = = = = −𝟏𝟖. 𝟏𝟑𝟖𝟒𝐉/𝐠
𝑚 𝑛·𝑀 𝑀 16.04276g/mol

1 𝑊
𝛼≈− ·
𝑃 · 𝑉0 ∆𝑇
𝑛 · 𝑅 · 𝑇0
𝑉0 =
𝑃
1 𝑊 1 −8729.7J
𝛼≈− · =− · = 𝟑. 𝟒𝟕𝟎𝟒 · 𝟏𝟎−𝟑 𝐊 −𝟏
𝑛 · 𝑅 · 𝑇0 ∆𝑇 (30mol) · [8.314J/(mol · K)] · (288.15K) (50 − 15)K
 %𝛼 = 𝟎. 𝟑𝟒𝟕𝟎𝟒%/𝐊

(b) Ecuación de Van der Waals:

𝑅·𝑇 𝑎
𝑃= − 2
𝑉𝑚 − 𝑏 𝑉𝑚
𝑎 = 0.229967679Pa · m6 /mol2
𝑏 = 4.30105 · 10−5 m3 /mol

Estado 0:
[8.314J/(mol · K)] · (15 + 273.15)K 0.229967679Pa · m6 /mol2
3039750Pa = −
𝑉𝑚,0 − 4.30105 · 10−5 m3 /mol 𝑉𝑚,0 2
Método de Newton-Raphson
(𝑘)
𝑉𝑚 𝑑𝐹 (𝑘) (𝑘+1) (𝑘+1) (𝑘)
(R)(𝑘)
𝑉𝑚
k 𝐹 (𝑘) ( ) 𝑉𝑚 (m^3/mol) |𝑉𝑚 − 𝑉𝑚 | 𝑍 (𝑘)
(m^3/mol) 𝑑𝑉𝑚 (m^3/mol)

0 0.00078812 194775.4352 3375548582 0.0007304152868 5.7702E-05 0.92678517250 -0.00005770186

1 0.00073042 -14307.13529 3889661821 0.0007340935333 3.6782E-06 0.93145230427 -0.00005402361
2 0.00073409 -66.68069527 3853489544 0.0007341108373 1.7304E-08 0.93147426037 -0.00005400631
3 0.00073411 -0.001461983 3853320569 0.0007341108377 3.7941E-13 0.93147426085 -0.00005400631
4 0.00073411 0 3853320566 0.0007341108377 0 0.93147426085 -0.00005400631

Estado 1:
[8.314J/(mol · K)] · (50 + 273.15)K 0.229967679Pa · m6 /mol2
3039750Pa = −
𝑉𝑚,1 − 4.30105 · 10−5 m3 /mol 𝑉𝑚,1 2
Método de Newton-Raphson
(𝑘)
𝑉𝑚 𝑑𝐹 (𝑘) (𝑘+1) (𝑘+1) (𝑘)
(R)(𝑘)
𝑉𝑚
k 𝐹 (𝑘) ( ) 𝑉𝑚 (m3/mol) |𝑉𝑚 − 𝑉𝑚 | 𝑍 (𝑘)
(m3/mol) 𝑑𝑉𝑚 (m^3/mol)
0 0.00088385 138894.4488 3133935718 0.0008395259198 4.4319E-05 0.94985605583 -0.00004431950
1 0.00083953 -6992.067643 3457419926 0.0008415482566 2.0223E-06 0.95214416729 -0.00004229716
2 0.00084155 -16.0269415 3441588197 0.0008415529134 4.6568E-09 0.95214943614 -0.00004229250
3 0.00084155 -8.45914E-05 3441551867 0.0008415529135 2.4579E-14 0.95214943616 -0.00004229250
4 0.00084155 0 3441551866 0.0008415529135 0 0.95214943616 -0.00004229250

𝑑𝑊𝑚 = −𝑃 · 𝑑𝑉𝑚
𝑉1
𝑊𝑚 = −𝑃 ∫ 𝑑𝑉𝑚 = −𝑃 · (𝑉1 − 𝑉0 ) =
𝑉0
𝑊𝑚 = −(3039750Pa) · (0.0008415529135 − 0.0007341108377)m3 /mol = −𝟑𝟐𝟔. 𝟓𝟗𝟕𝟎𝟒𝟗𝟖𝐉/𝐦𝐨𝐥

𝑊 = 𝑛 · 𝑊𝑚 = 30mol · (−326.5970498J/mol) = −𝟗𝟕𝟗𝟕. 𝟗𝟏𝟏𝟒𝟗𝟒𝐉

𝑊𝑚 −326.5970498J/mol
𝑤= = = −𝟐𝟎. 𝟑𝟓𝟕𝟗𝟎𝟗𝟏𝐉/𝐠
𝑀 16.04276g/mol

1 ∆𝑉𝑚 1 (0.0008415529135 − 0.0007341108377)m3 /mol

𝛼≈ · = · = 𝟎. 𝟎𝟎𝟒𝟏𝟖𝟏𝟔𝟐𝟏𝐊 −𝟏
𝑉𝑚,0 ∆𝑇 0.0007341108377m3 /mol (50 − 15)K

(c) Ecuación de Redlich-Kwong:

𝑅·𝑇 𝑎
𝑃= −
𝑉𝑚 − 𝑏 √𝑇 · 𝑉𝑚 · (𝑉𝑚 + 𝑏)
𝑎 = 3.216570904Pa · m6 · K 0.5 /mol2
𝑏 = 2.98114 · 10−5 m3 /mol
 Estado 0:
[8.314J/(mol · K)] · (15 + 273.15)K 3.216570904Pa · m6 · K 0.5 /mol2
3039750Pa = −
𝑉𝑚,0 − 2.98114 · 10−5 m3 /mol √(15 + 273.15)K · 𝑉𝑚,0 · (𝑉𝑚,0 + 2.98114 · 10−5 m3 /mol)
Método de Newton-Raphson
(𝑘)
𝑉𝑚 𝑑𝐹 (𝑘) (𝑘+1) (𝑘+1) (𝑘)
(R)(𝑘)
𝑉𝑚
k 𝐹 (𝑘) ( ) 𝑉𝑚 (m^3/mol) |𝑉𝑚 − 𝑉𝑚 | 𝑍 (𝑘)
(m^3/mol) 𝑑𝑉𝑚 (m^3/mol)

0 0.0007881 197563.0579 3433830384 0.0007305828389 5.7534E-05 0.92699777054 -5.75343E-05

1 0.0007306 -8765.14231 3962925157 0.0007327946249 2.2118E-06 0.92980418832 -5.53225E-05
2 0.0007328 -287.245539 3940380252 0.0007328675228 7.2898E-08 0.92989668463 -5.52496E-05
3 0.0007329 -8.61741953 3939640488 0.0007328697102 2.1874E-09 0.92989946006 -5.52474E-05
4 0.0007329 -0.25773501 3939618294 0.0007328697756 6.5421E-11 0.92989954307 -5.52474E-05
5 0.0007329 -0.00770779 3939617630 0.0007328697776 1.9565E-12 0.92989954555 -5.52474E-05
6 0.0007329 -0.00023051 3939617610 0.0007328697776 5.851E-14 0.92989954562 -5.52474E-05
7 0.0007329 -6.8935E-06 3939617610 0.0007328697776 1.7498E-15 0.92989954563 -5.52474E-05
8 0.0007329 -2.0629E-07 3939617610 0.0007328697776 5.2367E-17 0.92989954563 -5.52474E-05
9 0.0007329 -6.17E-09 3939617610 0.0007328697776 1.5179E-18 0.92989954563 -5.52474E-05
10 0.0007329 0 3939617610 0.0007328697776 0 0.92989954563 -5.52474E-05

Estado 1:
[8.314J/(mol · K)] · (50 + 273.15)K 3.216570904Pa · m6 · K 0.5 /mol2
3039750Pa = −
𝑉𝑚,1 − 2.98114 · 10−5 m3 /mol √(50 + 273.15)K · 𝑉𝑚,1 · (𝑉𝑚,1 + 2.98114 · 10−5 m3 /mol)
Método de Newton-Raphson
(𝑘)
𝑉𝑚 𝑑𝐹 (𝑘) (𝑘+1) (𝑘+1) (𝑘)
(R)(𝑘)
𝑉𝑚
k 𝐹 (𝑘) ( ) 𝑉𝑚 (m^3/mol) |𝑉𝑚 − 𝑉𝑚 | 𝑍 (𝑘)
(m^3/mol) 𝑑𝑉𝑚 (m^3/mol)
0 0.0008838 130942.5074 3190305835 0.0008428015420 4.1044E-05 0.95356215888 -4.10439E-05
1 0.0008428 -3781.90035 3497341225 0.0008438829064 1.0814E-06 0.95478563575 -3.99625E-05
2 0.0008439 -73.2423413 3488691314 0.0008439039006 2.0994E-08 0.95480938901 -3.99415E-05
3 0.0008439 -1.3293924 3488523699 0.0008439042817 3.8108E-10 0.95480982017 -3.99411E-05
4 0.0008439 -0.02409785 3488520657 0.0008439042886 6.9078E-12 0.95480982799 -3.99411E-05
5 0.0008439 -0.00043681 3488520601 0.0008439042887 1.2521E-13 0.95480982813 -3.99411E-05
6 0.0008439 -7.918E-06 3488520600 0.0008439042887 2.2698E-15 0.95480982813 -3.99411E-05
7 0.0008439 -1.4325E-07 3488520600 0.0008439042887 4.1091E-17 0.95480982813 -3.99411E-05
8 0.0008439 -2.3283E-09 3488520600 0.0008439042887 6.5052E-19 0.95480982813 -3.99411E-05
9 0.0008439 -4.3656E-10 3488520600 0.0008439042887 1.0842E-19 0.95480982813 -3.99411E-05
10 0.0008439 0 3488520600 0.0008439042887 0 0.95480982813 -3.99411E-05

𝑑𝑊𝑚 = −𝑃 · 𝑑𝑉𝑚
𝑉1
𝑊𝑚 = −𝑃 ∫ 𝑑𝑉𝑚 = −𝑃 · (𝑉𝑚,1 − 𝑉𝑚,0 ) =
𝑉0
𝑊𝑚 = −(3039750Pa) · (0.0008439042887 − 0.0007328697776)m3 /mol = −𝟑𝟑𝟕. 𝟓𝟏𝟕𝟏𝟓𝟓𝟏𝐉/𝐦𝐨𝐥

𝑊 = 𝑛 · 𝑊𝑚 = 30mol · (−326.5970498J/mol) = −𝟏𝟎𝟏𝟐𝟓. 𝟓𝟏𝟒𝟔𝟓𝐉

𝑊𝑚 −326.5970498J/mol
𝑤= = = −𝟐𝟏. 𝟎𝟑𝟖𝟓𝟗𝟔𝟓𝟒𝐉/𝐠
𝑀 16.04276g/mol

1 ∆𝑉𝑚 1 (0.0008439042887 − 0.0007328697776)m3 /mol

𝛼≈ · = · = 𝟎. 𝟎𝟎𝟒𝟑𝟐𝟖𝟕𝟓𝟔𝐊 −𝟏
𝑉𝑚,0 ∆𝑇 0.0007328697776m3 /mol (50 − 15)K
(d) Primer Virial
1 𝐵
𝑃 =𝑅·𝑇·( + 2)
𝑉𝑚 𝑉𝑚
𝐵0 = −0.000045912715m3 /mol
𝐵1 = −0.000033309842m3 /mol

Estado 0:
1 0.000045912715m3 /mol
3039750Pa = [8.314J/(mol · K)] · (15 + 273.15)K · ( − )
𝑉𝑚,0 𝑉𝑚,0 2
Método de Newton-Raphson
(𝑘)
𝑉𝑚 𝑑𝐹 (𝑘) (𝑘+1) (𝑘+1) (𝑘)
(R)(𝑘)
𝑉𝑚
k 𝐹 (𝑘) ( ) 𝑉𝑚 (m^3/mol) |𝑉𝑚 − 𝑉𝑚 | 𝑍 (𝑘)
(m^3/mol) 𝑑𝑉𝑚 (m^3/mol)
0 0.0007881 177084.3035 3407591626 0.0007361495640 5.19676E-05 0.93406109234 -0.000051968
1 0.0007361 -11618.55468 3869321931 0.0007391523006 3.00274E-06 0.93787110540 -0.000048965
2 0.0007392 -43.84965998 3840170259 0.0007391637193 1.14187E-08 0.93788559395 -0.000048953
3 0.0007392 -0.00062935 3840060028 0.0007391637194 1.63891E-13 0.93788559416 -0.000048953
4 0.0007392 0 3840060027 0.0007391637194 0 0.93788559416 -0.000048953

Estado 1:
1 0.000033309842m3 /mol
3039750Pa = [8.314J/(mol · K)] · (50 + 273.15)K · ( − )
𝑉𝑚,0 𝑉𝑚,0 2
Método de Newton-Raphson
(𝑘)
𝑉𝑚 𝑑𝐹 (𝑘) (𝑘+1) (𝑘+1) (𝑘)
(R)(𝑘)
𝑉𝑚
k 𝐹 (𝑘) ( ) 𝑉𝑚 (m^3/mol) |𝑉𝑚 − 𝑉𝑚 | 𝑍 (𝑘)
(m^3/mol) 𝑑𝑉𝑚 (m^3/mol)

0 0.0008838 114560.2963 3180001118 0.0008478201772 3.60252E-05 0.95924034098 -0.000036025

1 0.0008478 -4661.007772 3444018256 0.0008491735404 1.35336E-06 0.96077156266 -0.000034672
2 0.0008492 -7.112203554 3433515845 0.0008491756118 2.07141E-09 0.96077390629 -0.000034670
3 0.0008492 -1.66102E-05 3433499808 0.0008491756119 4.83771E-15 0.96077390630 -0.000034670
4 0.0008492 -3.49246E-10 3433499808 0.0008491756119 1.0842E-19 0.96077390630 -0.000034670
5 0.0008492 0 3433499808 0.0008491756119 0 0.96077390630 -0.000034670

𝑑𝑊𝑚 = −𝑃 · 𝑑𝑉𝑚
𝑉1
𝑊𝑚 = −𝑃 ∫ 𝑑𝑉𝑚 = −𝑃 · (𝑉𝑚,1 − 𝑉𝑚,0 ) =
𝑉0
𝑊𝑚 = −(3039750Pa) · (0.0008491756119 − 0.0007391637194)m3 /mol = −𝟑𝟑𝟒. 𝟒𝟎𝟖𝟔𝟓𝐉/𝐦𝐨𝐥

𝑊 = 𝑛 · 𝑊𝑚 = 30mol · (−334.40865J/mol) = −𝟏𝟎𝟎𝟑𝟐. 𝟐𝟓𝟗𝟓𝟎𝟎𝟓𝐉

𝑊𝑚 −334.40865J/mol
𝑤= = = −𝟐𝟎. 𝟖𝟒𝟒𝟖𝟑𝟐𝟖𝐉/𝐠
𝑀 16.04276g/mol

1 ∆𝑉𝑚 1 (0.0008491756119 − 0.0007391637194)m3 /mol

𝛼≈ · = · = 𝟎. 𝟎𝟎𝟒𝟐𝟓𝟐𝟑𝟔𝟗𝐊 −𝟏
𝑉𝑚,0 ∆𝑇 0.0007391637194m3 /mol (50 − 15)K

(e) Ecuación de Soave-Redlich-Kwong:

𝑅·𝑇 𝐴
𝑃= −
𝑉𝑚 − 𝑏 𝑉𝑚 · (𝑏 + 𝑉𝑚 )
𝑎 = 0.233023012Pa · m6 /mol2
 𝑏 = 2.98114 · 10−5 m3 /mol
𝑚 = 0.498862656
𝛼0 = 0.88540325
𝛼1 = 0.849213919
𝐴0 = 0.206319332Pa · m6 /mol2
𝐴1 = 0.197886386Pa · m6 /mol2

Estado 0:
[8.314J/(mol · K)] · (15 + 273.15)K 0.206319332Pa · m6 /mol2
3039750Pa = −
𝑉𝑚,0 − 2.98114 · 10−5 m3 /mol 𝑉𝑚,0 · (2.98114 · 10−5 m3 /mol + 𝑉𝑚,0 )
Método de Newton-Raphson
(𝑘)
𝑉𝑚 𝑑𝐹 (𝑘) (𝑘+1) (𝑘+1) (𝑘) 𝑉𝑚
(R)(𝑘)
k 𝐹 (𝑘) ( ) 𝑉𝑚 (m^3/mol) |𝑉𝑚 − 𝑉𝑚 | 𝑍 (𝑘)
(m^3/mol) 𝑑𝑉𝑚 (m^3/mol)

0 0.00078812 -439563.979 4963615560 0.0008766743646423760 8.85572E-05 1.1123656 8.85572E-05

1 0.00087667 -48757.8796 3922977906 0.0008891031574418330 1.24288E-05 1.1281358 0.000100986
2 0.0008891 -749.195609 3803337577 0.0008893001411682130 1.96984E-07 1.1283857 0.000101183
3 0.0008893 -0.18245957 3801485266 0.0008893001891651280 4.79969E-11 1.1283858 0.000101183
4 0.0008893 -1.1089E-08 3801484815 0.0008893001891651310 2.92735E-18 1.1283858 0.000101183
5 0.0008893 3.20142E-10 3801484815 0.0008893001891651310 1.0842E-19 1.1283858 0.000101183
6 0.0008893 0 3801484815 0.0008893001891651310 0 1.1283858 0.000101183

Estado 1:
[8.314J/(mol · K)] · (15 + 273.15)K 0.197886386Pa · m6 /mol2
3039750Pa = −
𝑉𝑚,1 − 2.98114 · 10−5 m3 /mol 𝑉𝑚,1 · (2.98114 · 10−5 m3 /mol + 𝑉𝑚,0 )

Método de Newton-Raphson
(𝑘)
𝑉𝑚 𝑑𝐹 (𝑘) (𝑘+1) (𝑘+1) (𝑘) 𝑉𝑚
(R)(𝑘)
k 𝐹 (𝑘) ( ) 𝑉𝑚 (m^3/mol) |𝑉𝑚 − 𝑉𝑚 | 𝑍 (𝑘)
(m^3/mol) 𝑑𝑉𝑚 (m^3/mol)

0 0.00088385 -351158.293 4228991492 0.0009668813571410820 8.30359E-05 1.0939485 8.30359E-05

1 0.00096688 -32689.288 3478041255 0.0009762801208848510 9.39876E-06 1.1045824 9.24347E-05
2 0.00097628 -341.338814 3405783074 0.0009763803441833250 1.00223E-07 1.1046958 9.25349E-05
3 0.00097638 -0.03800826 3405024645 0.0009763803553457300 1.11624E-11 1.1046958 9.25349E-05
4 0.00097638 0 3405024560 0.0009763803553457300 0 1.1046958 9.25349E-05

𝑑𝑊𝑚 = −𝑃 · 𝑑𝑉𝑚
𝑉1
𝑊𝑚 = −𝑃 ∫ 𝑑𝑉𝑚 = −𝑃 · (𝑉𝑚,1 − 𝑉𝑚,0 ) =
𝑉0
𝑊𝑚 = −(3039750Pa) · (0.0009763803553457300 − 0.0008893001891651310)m3 /mol = −𝟐𝟔𝟒. 𝟕𝟎𝟏𝟗𝟑𝟓𝟏𝐉/𝐦𝐨𝐥

𝑊 = 𝑛 · 𝑊𝑚 = 30mol · (−264.7019351J/mol) = −𝟕𝟗𝟒𝟏. 𝟎𝟓𝟖𝟎𝟓𝟒𝐉

𝑊𝑚 −264.7019351J/mol
𝑤= = = −𝟏𝟔. 𝟒𝟗𝟗𝟕𝟕𝟓𝟑𝐉/𝐠
𝑀 16.04276g/mol

1 ∆𝑉𝑚
𝛼≈ · =
𝑉𝑚,0 ∆𝑇
1 (0.0009763803553457300 − 0.0008893001891651310)m3 /mol
𝛼≈ 3
· = 𝟎. 𝟎𝟎𝟒𝟐𝟓𝟐𝟑𝟔𝟗𝐊 −𝟏
0.0008893001891651310m /mol (50 − 15)K