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Proyecto de ecuaciones de Van der Waals para cambios de estado

Físico química I
Sofía Terán y Paul Castro
001301329 y 00132426

Question 1

Choose two different substances mentioned in table 1 of the sheet tables. Copy their
names into sheet pvT-calc. Calculate for these substances the van der Waals parameters a and b,
by copying the critical temperature Tc, the critical pressure pc and the critical molar volume vc
of these substances into sheet pvT-calc.


En las tablas encontradas en las hojas de Excel pvT-cal se tomaron como base los datos de la Tc,
Pc y Vc de n-butano y n-pentano.

Tabla 1. Constantes a y b de Van der Waals, temperatura, presión y volumen crítico para n-
butano y n-pentano

Nombre de sustancia n-butano n-pentano

Tc [K] 3.37 x106 3.80 x106

Pc [Pa] 469.6 425.2

Vc [m3.mol-1] 3.04 x10-4 2.55 x10-4

Van der Waals a 1.91 x1000 7.09 x10-1

Van der Waals b 1.45x10-4 8.23 x10-5

Question 2


Calculate, using sheet pvT-calc, for the two substances chosen in question 1, how the
pressure depends on the molar volume. Do this for a few temperatures. Consider for instance
temperatures that are above, slightly above, and slightly below the critical temperature. Compare
the results you have obtained for the ideal gas equation of state and the Van der Waals equation
of state. What do you conclude?

n-Pentano:
Figura 1. Presión vs volumen molar para el n- pentano a T=250K

Figura 2. Presión vs volumen molar para el n- pentano a T=435K

Figura 3. Presión vs volumen molar para el n- pentano a T=700K


n-Butano

Figura 4. Presión vs volumen molar para el n- Butano a T=250K

Figura 5. Presión vs volumen molar para el n- Butano a T=303K


Figura 6. Presión vs volumen molar para el n- Butano a T=500K

Cuando la temperatura está por debajo de la Tc de cada gas, la gráfica de la ecuación de


Van der Waals se encuentra muy distante de la ecuación del gas ideal. No obstante, mientras la
temperatura se acerca a Tc se observa una textura en la curva con puntos de inflexión donde su
derivada es =0 siendo un mínimo global. Finalmente, cuando el punto de la temperatura es
superior a la Tc, la ecuación de Van der Waals se asemeja a la ecuación del gas ideal. Es así,
como inferimos que los gases reales a altas temperaturas se comportara de manera similar a un
gas ideal debido a la falta de interacción entre moléculas a altas velocidades.

Question 3

Now we are going to use sheet Maxwell to perform the Maxwell construction for the two
substances you have chosen in question 1. For a given temperature the liquid phase is
equilibrium with the vapour phase when Area 1=Area 2.
● Calculate for each of the two substances you have chosen for four temperatures the
pressure p and the molar volumes v at which the liquid phase is in equilibrium with the
gas phase. The Maxwell construction is good enough when the difference between areas
1 and 2 is less than 2%. Do also write down the temperatures at which you have
performed these calculations!
● Add to these data also critical temperature, critical pressure and critical volume you have
calculated in question 1.
● Construct using these data a p-v phase diagram in sheet worksheet. This phase diagram
has several names: the gas-liquid coexistence curve or the binodal or the saturation curve
or the equilibrium curve.

Tabla 2. Diferencias de áreas para n- butano y n-pentano con temperaturas superiores a la Tc.
Nombre de la n-pentano n-butano
sustancia

TC [K] 469.60 304.20

PC [Pa] 469.6 425.2

VC [m3.mol-1] 3.04 x10-4 2.55 x10-4

T [K] 400 280

P(trial) [Pa] 1715989 2704300

Área 1 2.1x102 3.68x101t

Área 2 2.1x102 3.68x101

Diferencia de Áreas. 0.02% 0.02%

Figura 7. Curva de coexistencia gas-liquido para n-butano


Figura 8. Curva de coexistencia gas-liquido para n-butano

Question 4

How can you derive the liquid-gas coexistence curve (in a p-T diagram) using the data you
have obtained in question 3. Plot this curve in sheet worksheet for one of the substances. When compare
this curve qualitatively with figure 2, which branch of figure 2 have you just plotted

Tabla 3. Temperaturas y presiones para n-Pentano.

P [Pa] T [K]

3101162 460
2835319 450

2463288 435

2346298 430

2015987 415

1912687 410

1716040 400

1697120 399

Figura 9. Diagrama p-t para n-Pentano

Podemos ver que los datos no generan una línea recta sino, unas leves curvaturas a lo
larga de esta. Usando la gráfica como base podemos observar que nos encontramos en la sección
de líquido-gas ya que estamos trabajando con temperaturas altas y presiones altas.

Question 5
Plot in sheet worksheet for two substances, the reduced pressure pr as a function of the
reduced molar volume r at the same reduced temperature Tr in a single graph. Take the critical
constants as calculated by the program in sheet pvT-calc.

Figura 10. Pr [Pa]vs Tr [K] y Pr [Pa] vs Vr [m3.mol-1] para n-Pentano

Figura 10. Pr [Pa]vs Tr [K] y Pr [Pa] vs Vr [m3.mol-1] para n-Butano


Question 6
Plot in sheet worksheet for two substances, the reduced pressure pr as a function of the reduced molar
volume r for the pressures and volumes of the coexistence curve.

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