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Wyatt Tenhaeff Milo Koretsky Department of Chemical Engineering Oregon State University koretsm@engr.orst.edu

1

**4.1. (a) Yes, the form of the equation is reasonable. This can be rewritten:
**

PA+ = RT a − n v A+ v A+

It is equivalent to Pv = RT , except the pressure term has been corrected to account for the ions’ intermolecular forces. The coulombic forces between the gas molecules affect the system pressure. This modification is similar to the van der Waals equation. Since we are limited to 1 parameter, we need to choose the most important interaction. Since net electric point charges exert very strong forces, this effect will be more important than size. (b) The sign should be negative for a because the positively charged gas molecules repel each other due to coulombic forces. Therefore, the system pressure increases, i.e.,:

PA+ > Pideal

Coulombic forces are much stronger than van der Waals interactions, so a will be large – much larger than a values for the van der Waals EOS. (c) Coulombic repulsion is the primary intermolecular force present in the gas. Coulombic potential energy is proportional to r-1. v is proportional to r3, so the coulombic potential goes as v-1/3. Therefore,

n=

1 3

a must have must have the following units to maintain dimensional homogeneity with the pressure term:

⎡ a ⎤ ⎡N⎤ ⎡ J ⎤ = = 1/ 3 2 3 ⎢ ⎣m ⎥ ⎦ ⎣m ⎥ ⎦ ⎢ ⎦ ⎢ ⎣v ⎥

so

[a] = ⎡ ⎢

J ⎤ 1/3 ⎥ ⎣ m ⋅ mol ⎦

2

2

4.2 The attractive interactions are described by van der Waals forces. For both O2 and propane, the dipole moments are zero. Therefore, the expression for the interactions reduce to Γ=−

3 α iα j 2 r6

⎛ Ii I j ⎜ ⎜ Ii + I j ⎝

⎞ ⎟ ⎟ ⎠

From Table 4.1:

I a = 12.07 [eV ] = 1.933 × 10 −11 [erg ]

I b = 10.94 [eV] = 1.753 × 10 −11 [erg] Now obtain the requested expressions:

3 16 × 10 − 25 cm 3 Γaa = − 2 r6

Γaa = − 3.71 × 10 −59 r

6

(

[ ]) ⎡⎢ (1.933 ×10

2

6

[cm

erg 1.933 × 10 −11 erg ⎤ ⎥ ⎥ ⎢1.933 × 10 −11 erg + 1.933 × 10 −11 erg ⎦ ⎣

−11

)(

)

⋅ erg

]

Γab = − Γab =

3 16 × 10 − 25 cm 3 62.9 × 10 − 25 cm 3 2 r6

6

(

[ ])(

6

[ ]) ⎡⎢ (1.933 ×10

)(

− 1.39 × 10 −58 r

[cm

⋅ erg

]

−11

erg 1.753 × 10 −11 erg ⎤ ⎥ −11 erg + 1.753 × 10 −11 erg ⎥ ⎢ ⎣ 1.933 × 10 ⎦

−11

)(

)

3 62.9 × 10 − 25 cm 3 Γbb = − 2 r6

(

[ ]) ⎡⎢ (1.753 ×10

2

Γbb =

(b) Calculation:

− 5.20 × 10 −58 r

6

[cm

6

⋅ erg

]

erg 1.753 × 10 −11 erg ⎤ ⎥ −11 erg + 1.753 × 10 −11 erg ⎥ ⎢ ⎣1.753 × 10 ⎦

)

⎞ ⎞⎛ − 5.20 × 10 − 58 ⎛ − 3.71 × 10 − 59 6 ⎜ cm ⋅ erg ⎟⎜ cm 6 ⋅ erg ⎟ Γaa Γbb = ⎟ ⎟⎜ ⎜ r6 r6 ⎠ ⎠⎝ ⎝

[

]

[

]

3

6 Γaa Γbb = − 1. The values are equal because the ionization energies are (c) An expression for the average intermolecular attraction in the mixture can be found using the mixing rules 2 2 Γmix = y a Γaa + 2 y a yb Γab + yb Γbb 2 2 − 3.20 × 10 −58 yb Γmix = cm 6 ⋅ erg 6 r ( )[ ] 4 .39 × 10 −58 [cm 6 ] The value of similar.⋅ erg r Note: Disregarded the positive value.71 × 10 −59 y a + 1.39 × 10 −58 y a yb + 5. Γaa Γbb is equal to Γab .

3 (a) 300 K.4.8 1 yBClH2 5 .6 0 0. 10 atm. the kinetic energy of the molecules (speed) is greater. 20 atm.7 0. (b) 1000 K. the compressibility factor is closer to unity. the plot may look like the following. The intermolecular distance of molecules is greater at lower pressures. thus.9 0. (c) Let subscript “1” denote BClH2 and “2” denote H2. The molecules interact less.8 z zBClH2 lowest 0. zH2 close to 1 1 quadradic.4 0. fewer intermolecular interactions exist. we calculate the compressibility factor as follows B z = 1 + mix v where 2 Bmix = y12 B1 + 2 y1 y2 B12 + y 2 B2 Since BClH2 is polar and H2 is non-polar and small B1 >> Bmix > B2 Therefore. which cause less deviation from ideality. At higher temperatures.2 0. For the mixture.6 0. Therefore. not linear 0.

4.15 K )⎟ 2 ⎜ ⎟ 3 ⎣ ⎦⎠ 27 (RTc ) 27 ⎝ ⎝ ⎠ = 3. but it should be noted that more modern EOSs will give more accurate results.0 × 10 ⎢ − 1. a is 5 times the a value in Part (b).65 º C ⎡ m3 ⎤ ⎢ mol ⎥ ⎣ ⎦ The styrene will not decompose at this temperature.0 × 10 −4 ⎜ ⎝ ⎡ m3 ⎤ ⎞ ⎢ mol ⎥ ⎟ ⎟ ⎣ ⎦⎠ 2 ⎛ ⎡ J ⎤⎞ ⎜ ⎜ 8. 6 . the order of importance is as follows dispersion > dipole . the b parameter for the reduced polymer chain is 5 times the b value from Part (b).314 ⎢ mol ⋅ K ⎥ ⎟ ⎟T ⎣ ⎦⎠ ⎝ 5 10 × 10 [Pa ] = 3 −4 ⎡ m ⎤ 3. For the 5-monomer long polymer chain. Dispersion is the controlling intermolecular force in this system.dipole ≅ induction The van der Waals EOS is appropriate since it accounts for the occupied molar volume and intermolecular forces.13 ⎢ 2 ⎥ ⎣ mol ⎦ ⎛ ⎜ 3. P= RT a − v − b v2 − ⎡ J ⋅ m3 ⎤ 3. (c) The a parameter is related to attractive intermolecular forces.15 K ) ⎜ 8. The b parameter is also related to the size of the molecule since it accounts for the volume occupied by the molecules. Since styrene monomers are essentially non-polar. (b) Use critical data to calculate the a and b parameters: ⎛⎛ ⎞ ⎡ J ⎤⎞ ⎜⎜ ⎜ 8.13 ⎡ J ⋅ m ⎤ = a= ⎢ ⎥ 2 64 Pc 64 39 × 105 [Pa ] mol ⎢ ⎥ ⎣ ⎦ b= RTc = 8 Pc ⎛ ⎡ J ⎤⎞ ⎜ ⎟(647. Again.72 × 10 −4 ⎥ ⎣ mol ⎦ ∴ T = 550.314 ⎢ mol ⋅ K ⎥ ⎟ ⎦⎠ ⎣ ⎝ 8 39 × 105 [Pa ] 2 ( ) ⎡ m3 ⎤ = 1.72 × 10 − 4 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ Now we can use the van der Waals EOS to solve for temperature.314 ⎢ mol ⋅ K ⎥ ⎟ ⎟(647.4 (a) The intermolecular attractions and volume occupied by the styrene monomers will contribute to the deviations from ideality.8 K = 277. and its magnitude is directly related to the size of the molecules (polarizability component of dispersion).

6 10 ⎥ ⎢ mol ⎥ ⎜ 1.⎡ J ⋅ m3 ⎤ a = 15. then there can only be 20 moles of the 5-monomer long polymer chain. ⎡ m3 ⎤ v = 1. 65 ⎜ ⎢ mol 2 ⎥ ⎜ 8.314 ⎢ mol ⋅ K ⎥ ⎟ ⎟T ⎣ ⎦⎠ ⎝ ⎣ ⎦ 5 − 10 × 10 [Pa ] = 2 3 3 3 ⎡ ⎤ ⎡ ⎤ m m ⎛ ⎞ −4 −3 ⎡ m ⎤ − × 1.26 º C Decomposition will occur.5 × 10 −3 ⎢ 8 . 7 . Therefore.5 × 10 ⎢ ⎥⎟ ⎟ ⎣ mol ⎦ ⎣ ⎦ ⎜ mol ⎣ ⎦⎠ ⎝ T = 612.5 × 10 − 3 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ and ⎡ J ⋅ m3 ⎤ ⎛ ⎡ J ⎤⎞ 15 .41K = 339.6 × 10 − 4 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ (d) We must realize that if we initially believed there were 100 moles of styrene in the reactor.65 ⎢ 2 ⎥ ⎣ mol ⎦ ⎡ m3 ⎤ b = 8.

4 × 10 −25 cm 3 [ ] α calculated (x 1025 cm3) 63.3 1.3 The values of C3 H 8 .6 64.8 0. the polarizability of the chlorine atom can be found.1 3. the polarizabilities of C 4 H10 and C 2 H 5Cl will be calculated. Method 1.8 65. and the level of complexity varies for each method.1 × 10 − 25 cm 3 ( [ ]) ( [ ]) [ ] 8 . CH 2Cl2 .4 × 10 − 25 cm 3 + 10 3. and compared to the values given.6 All agree reasonably well. To illustrate the principles in Chapter 4. CH 3Cl .3 α reported (x 1025 cm3) 62. the polarizabilities of individual atoms are additive. αC 4 H 10 = 4 11. Now. Polarizability of each atom The polarizability of a molecule scales with the number of atoms. Species C3H8 CH3Cl CH2Cl2 CHCl3 % Difference 0. solution of the following system of equations 1α C + 4α H = 1α CH 4 2α C + 6α H = 1α C2 H 6 gives α C = 11. two of the simplest solution methods will be illustrated.5 85. α Cl = 23.4.9 45.4 45.5 There are many ways to solve this problem.65 × 10 − 25 cm 3 = 82.8 82. 1α C + 4α Cl = 1α CCl 4 Therefore.65 × 10 − 25 [ ] [cm ] 3 Now.4 × 10 −25 cm 3 α H = 3. Using the first two molecules. For chloroform. and CHCl3 are calculated with the polarizabilities found above as follows.

6 All agree reasonably well.8 65.3 1.4 × 10 − 25 cm 3 = 64. and compared to the values given.1 × 10 − 25 cm 3 ( [ ]) ( [ ]) [ ] 9 .3 % Difference 0. and CHCl3 are calculated with the polarizabilities found above as follows. instead of the atoms.25 × 10 − 25 cm 3 4 [ ] [ ] The values of C3 H 8 . we calculate the molecules’ polarizabilities by adding the polarizability of each bond. For the methane molecule 4α C − H = 1α CH 4 ∴α C − H = 26 × 10 − 25 cm 3 = 6.5 85.9 45.5 × 10 − 25 cm 3 = 82. 1α C 4 H 10 = 3α C − C + 10α C − H αC 4 H 10 = 3 5.5 × 10 − 25 cm 3 4 [ ] [ ] To calculate the polarizability of a C-C bond. use ethane as follows: 6α C − H + α C − C = 1α C 2 H 6 ∴ α C − C = 44.1 3.6 64.7 × 10 − 25 cm 3 [ ] ( [ ]) [ ] The C-C and C-H polarizability calculated above predict the given polarizability of propane well. CH 2Cl2 . 4α C − Cl = 1α CCl 4 ∴ α C − Cl = 105 × 10 − 25 cm 3 = 26. Bond Polarizability For this method.5 × 10 − 25 cm 3 = 5.65 × 10 − 25 cm 3 + 1 23. The polarizability of C-Cl bonds is calculable with the polarizability of chloroform.4 45.αC 2 H 5 Cl = 2 11.7 × 10 − 25 cm 3 − 6 6.7 × 10 − 25 cm 3 + 10 6. the polarizabilities of C 4 H10 and C 2 H 5Cl will be calculated. CH 3Cl .8 0.4 × 10 − 25 cm 3 + 5 3.45 × 10 − 25 cm 3 ( [ ]) ( [ ]) ( [ ]) [ ] Method 2. This value predicts the polarizabilities of the other species in the table reasonably well.3 α reported (x 1025 cm3) 62.8 82. Species C3H8 CH3Cl CH2Cl2 CHCl3 α calculated (x 1025 cm3) 63. Now.

7 × 10 − 25 cm 3 + 5 6.45 × 10 − 25 cm 3 ( [ ]) ( [ ]) ( [ ]) [ ] Note both the atom method and the bond method yield identical results. 10 .1α C 2 H 5 Cl = 1α C − C + 5α C − H + 1α C − Cl αC 2 H 5 Cl = 1 5.25 × 10 − 25 cm 3 = 64. More accurate values for the polarizabilities can be calculated using more of the data given in the problem.5 × 10 − 25 cm 3 + 1 26.

butanol > ε diethyl ether 11 .butanol ≅ σ diethyl ether ≅ σ methyl ethyl ketone Methyl ethyl ketone and n-butanol are much more polar than diethyl ether due to their greater asymmetry. only dispersion forces are present. Because these are non-polar. ε scales with the magnitude of van der Waals interactions. so ε I > ε S > εO 2 2 2 (b) σ increases with molecular size. The polarizability scales with molecular size. but has two exposed electron pairs on the double-bonded oxygen. There is greater charge separation in the double bond of ketone. so their ε values are greater than diethyl ether’s. diatomic molecules. Diethylether and n-butanol have the same atomic formula and similar spatial conformations. we must consider the strength of dipole-dipole forces. Therefore. Now we must determine if there is greater attraction in n-butanol or methyl ethyl ketone. Ionization energy is approximately equal for each molecule. so ε methyl ethyl ketone > ε n . σ I > σS > σO 2 2 2 ε scales with magnitude of van der Waals interactions. Methyl ethyl ketone has fewer atoms. The size of the molecular electron orbital of methyl ethyl ketone is approximately equal to the sizes of diethyl ether and n-butanol. Therefore. so σ n . Dispersion forces depend on the first ionization potential and polarizability. Since induction and dispersion forces are similar in these molecules.6 (a) σ increases with molecular size.4. they should be about equal in size.

The intermolecular forces are greater in the isopropanol. Therefore. so the magnitude of molecular potential energy is greater. (b) The key to this phenomenon is hydrogen bonding. At 300 K and 30 bar. isopropanol and npentane are both liquids. the compressibility factor is smaller for n-pentane. hydrogen bonding does not play a significant role. The dispersion forces in n-pentane are stronger than the dipole-dipole forces of isopropanol. The potential energy has a negative value for attractive interactions.7 (a) At 30 bar. The hydrogen bonding and dipole-dipole interactions are present in isopropanol. Hence. Intermolecular attractions are greater. 12 .4. In the gas phase. is less at 30 bar. the water molecules are in closer proximity than they are at 20 bar. the internal energy. At 500 K and 30 bar. The molecular kinetic energy is identical since the temperature is the same. so the compressibility factor is smaller for isopropanol. the sum of kinetic and potential energies. and dispersion is present in n-pentane. both species are gases.

fewer possible configurations exist.4. (b) Internal energy will be greater for the ideal gas. The absolute values of the kinetic energies are identical at identical temperature: however. Entropy is a measure of possible molecular configurations or “randomness”. Internal energy value is the sum of potential and kinetic energies of the molecules. In the real gas. z will be less than one. 13 . (c) The entropy will be greater for the ideal gas. For real NH3. the compressibility factor is equal to one. the potential energy decreases for real NH3 due to attractive interactions . Ammonia has an electric dipole in which positive and negative charge are separated. which creates less randomness and lower entropy. the strong intermolecular forces (dipole-dipole and dispersion) cause the molar volume to decrease. thus.so the internal energy is less for the real NH3. intermolecular attractions are present. They outweigh the volume displaced by the physical size of NH3. Therefore. The intermolecular forces in the real gas cause the molecules to align so that the positive charge in one molecule is adjacent to a negative charge in a neighboring molecule to reduce potential energy.8 (a) Ideal: For ideal NH3.

(b) Entropy is a measure of randomness. so volume displacement becomes important. the strong intermolecular attractions decrease the molar volume. With Ne. The compressibility factor will be slightly greater than one. Therefore. However. The compressibility factor is greater for Ne. intermolecular interactions are relatively weak. In NH3. NH3 is asymmetrical. while Ne is symmetrical. The weak forces present in Ne have a much smaller effect. and we can guess that entropy is greater in NH3. Both species are gases at these conditions. The intermolecular attractions present in NH3 reduce the number of possible configurations. it is difficult to qualitatively show for which case the entropy is greater. so z is less than one.4. Since both species are gases.9 (a) We can determine which case has the higher compressibility factor by comparing the molar volumes at constant T and P. 14 . very weak intermolecular attractions are present. The asymmetry of NH3 results in more possible configurations that NH3 can have.

18 ×10−9 [m] 15 . Tr = 1. To estimate the distance between each atom.99 Pr = 0.314 ⎢ mol ⋅ K ⎥ ⎟ ⎟(300 K ) ⎦⎠ ⎣ ⎝ 25 × 105 [Pa ] = 9. At 300 K and 25 bar.513 From the generalized compressibility charts: z = 0.9859 ⎛ ⎡ J ⎤⎞ ⎜ ⎜ 8.10 (a) To find the average distance between the two atoms of Ar. v = 0. we can find the volume that each atom occupies.4.9859 Therefore.84 × 10 −4 ⎡ m3 ⎤ ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ ⎡ m3 ⎤ v = 1. The molar volume can be found from the compressibility factor.63 ×10 − 27 ⎢ ⎥ atom ⎢ ⎥ ⎣ ⎦ The second number was found by dividing the molar volume by Avogadro's number.63 × 10 − 27 m 3 ( )1 / 3 = 1. we note that the distance between molecules can be related to the volume by: r3 ∝ v Consider the geometry shown below: 3 v r Ar Ar A rough estimate of r is r = 1.

26 ⎡ kg ⎤ ⎜ ⎟⎜ m Ar = ⎜ ⎟ ⎜ 1 [mol Ar ] ⎟⎜ ⎜ 1000 [g ] ⎟ ⎟ = 6. The mass of an argon atom is calculated as follows ⎞⎛ 1 [kg ] ⎞ ⎛ 39. we get ( ) ΓAr − Ar = −1.18 × 10 − 7 [cm] .r = 11. London interactions are much more important.76 [eV] = 2.67 × 10 −11 ⎢ ⎥ ⎟ and mAr is the mass of an argon 2 ⎟ ⎜ ⎢ ⎣ kg ⋅ s ⎥ ⎦⎠ ⎝ atom.948 [g Ar] ⎞⎛ 1 [mol] . and gravitational effects can be neglected.93 × 10 −10 [erg] = −1.023 × 10 [atoms] ⎠⎝ ⎠ Using the distance calculated in Part (a).1 I Ar = 15.6 × 10 −25 cm 3 [ ] Using the distance calculated in Part (a) r = 1.93 × 10 −17 [J ] (d) The potential energy due to London interactions is around 10 35 times greater than the potential energy due to gravity. we get ΓG = −2.49 ×10 -52 [J ] (c) Equation 4.13 quantifies the potential energy due to London interactions ΓAr − Ar = − 3 α Arα Ar 2 r6 ⎛ I Ar I Ar ⎜ ⎜I +I Ar ⎝ Ar ⎞ ⎟ ⎟ ⎠ From Table 4. Clearly.52 × 10 -4 [erg] α Ar = 16.633 × 10 ⎢ 23 ⎟ ⎣ atom ⎥ ⎦ ⎝ ⎠⎝ 6.8 [A ] (b) The potential energy due to gravity can be calculated as follows ΓG = − G ⋅ m2 Ar r ⎛ ⎡ m2 ⎤ ⎞ where G is the gravitation constant ⎜ G = 6. 16 .

to match the first (LJ) potential to the second (exp) potential. we iterate on a spreadsheet. For this solution we choose equal well depths and equal values at Γ=1.000 and c2 = 11. Other choices may be just as valid. c1 and c2. you should realize that you have two parameters to fit and so must specify two features. we can rewrite the equation in dimensionless quantities: Γ* = where r* = Γ ⎡ 1 1 ⎤ =⎢ − ⎥ 12 6 4ε ⎢ ( ) ( ) r * r * ⎥ ⎣ ⎦ r σ We want to compare this to an exponential repulsive function * Γexp ⎡ ⎤ ⎛ c2 ⎞ 1 ⎥ ⎢ = c1 exp⎜ ⎜ *⎟ ⎟− ⎢ ⎝ r ⎠ r * 12 ⎥ ⎣ ⎦ ( ) We have two adjustable parameters.11 We want to compare the Lennard-Jones potential to one with an exponential repulsion term.4. the Lennard-Jones potential is ⎡⎛ σ ⎞12 ⎛ σ ⎞ 6 ⎤ Γ = 4ε ⎢⎜ ⎟ − ⎜ ⎟ ⎥ ⎝r⎠ ⎥ ⎢ ⎣⎝ r ⎠ ⎦ To simplify further analysis.8 This solution is shown at two magnifications in the plots on the following page: 17 .19. Using the above criteria. to get the solution: c1 = 143. As provided in the text. We need to choose reasonable criteria to specify. Equation 4.

The most stable configuration (the bottom of the well) occurs at a greater separation for the exp model.Potential functions 0.1 -0.1 Lennard-Jones exponential Potential functions 20 15 Lennard-Jones exponential 10 5 0 0.3 1. The two models are in reasonable qualitative agreement 18 .3 1 1.2 0.9 2 2.3 1.9 -0..1 1. it behaves more like the hard-sphere potential.8 1.6 1.3 0.5 1.6 1.9 We draw the following conclusions: 1.7 -5 1 1. The Lennard-Jones potential increases more steeply at small radii.7 1.2 -0. 3.e. i.1 0 0.4 1. 2.2 1.

77 × 10 −11 [erg] = −11.803 × 10 −10 Γ = 2. The interaction between the chlorine and sodium ions is Coulombic attraction.01 × 10 −11 [erg ] r 2.1 [eV] Γ=6 ( )( ) (d) QNa QCl Q Q Q Q Q Q + 12 Na Na + 8 Na Cl + 6 Na Na r r r r −10 4. Γ=6 QNa QCl 4.803 × 10 −10 esu =6 = −5.01 × 10 −11 [erg] + 12 (4.4.37 × 10 −12 [erg] = 4.803 × 10 −10 esu − 4.803 × 10 esu 4.3 [eV ] ( ( )( ) ) (b) Γ=6 QNa QCl Q Q + 12 Na Na r r Γ = −5.0 [eV] (c) esu )(4.60 [eV] Γ=6 ( )( ) 19 .77 × 10 [erg ] + 6 5.803 × 10 −10 esu − 4.803 × 10 −10 esu ) 3.12 (a) The bond strength of a sodium ion can be viewed as the amount of energy it would take to remove the sodium ion from the crystal lattice.803 × 10 −10 esu −11 Γ = −1.089 × 10 −11 [erg] = 13.76 × 10 -8 cm Γ = −31.90 × 10 -8 cm QNa QCl Q Q Q Q + 12 Na Na + 8 Na Cl r r r 4.78 × 10 -8 cm Γ = −1.089 × 10 −11 [erg] + 8 4.803 × 10 −10 esu Γ = 2.52 × 10 -8 cm Γ = 7.

Dispersion and dipole-dipole interactions are present in all five species listed.13 The boiling points of the halides depend upon the strength of intermolecular attractions. which manifests in larger dispersion forces. The magnitude of the dipole-dipole interactions is similar so the pertinent intermolecular force in these molecules is dispersion. Polarizabilities are greater in larger molecules. Therefore. The molecular size increases from left to right. 20 . The stronger the intermolecular attraction. the boiling point increases from left to right. the higher the boiling point.4.

4.19: to get ⎡⎛ σ ⎞12 ⎛ σ ⎞ 6 ⎤ Γ = 4ε ⎢⎜ ⎟ − ⎜ ⎟ ⎥ ⎝r⎠ ⎥ ⎢⎝ r ⎠ ⎣ ⎦ Differentiation with respect to r yields ⎡ 12 ⎛ σ ⎞12 6 ⎛ σ ⎞ 6 ⎤ dΓ = 4ε ⎢− ⎜ ⎟ + ⎜ ⎟ ⎥ = 0 dr r⎝r ⎠ ⎦ ⎢ r ⎝r⎠ ⎥ ⎣ where we set this derivative equal to zero to find the minimum.14 van der Waals forces hold the Xe atoms together in a molecule of Xe2.2: ε k and = 229 K σ = 4 .12σ = 4.60 A 21 . From Table 4. Solving gives 1 ⎛σ ⎞ ⎜ ⎟ = 2 ⎝r⎠ 6 or r = 6 2σ = 1.1 A We start with Equation 4. The potential energy can be quantified with the Lennard-Jones potential function. The bond length is the r value where the potential is a minimum.

the following table was created. these two molecules also have dipole-dipole and induction forces. the values of dipole moment and polarizability reported in Table 4.2 14.554 ⎡ m3 ⎤ b × 105 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ 2.40.74 3.85 α [cm x 1025] 3 Species He CH4 NH3 H2O 2.15 The data in the following table were taken from Table A. although slightly weaker in the ammonia and water. In fact.38 4.47 1. ammonia.3 Pc × 10 -5 [Pa ] 2.48 The van der Waals a parameter can be calculated using Equation 4.27 46.8 The values of a for helium is two orders of magnitude less than the other species since it only has weak dispersion forces (small atom.31 3. the strong dipole in water gives it the largest value The values of b are all of the same magnitude.425 0.1.39.00346 0. and water are of the same magnitude because the sums of the intermolecular attractions for each molecule are similar. as expected since b scales with size according to the number of atoms in the molecule. However. small α).1 Species He CH4 NH3 H2O Tc [K ] 5. b= RTc 8 Pc Using the data table and equations listed above. The values of a for methane.6 647.19 190. unlike methane.4.6 405.77 220. 27 (RTc )2 a= 64 Pc The van der Waals b parameter can be calculated using Equation 4.00 112. All three molecules have comparable dispersion forces.1 26 22.1 are also included. ⎡ J ⋅ m3 ⎤ a⎢ ⎥ 2 mol ⎢ ⎥ ⎣ ⎦ 0.230 0. Size of Molecules: ∴ Value of b: CH 4 > NH 3 > H 2O > He bCH 4 > bNH 3 > bH 2O > bHe 22 .05 µ [D] 0 0 1.

2 are included along with the percent difference.5 3.6 80. ⎣ mol ⋅ K ⎥ ⎦ The equation from page 186 can be rewritten to calculate σ .27 3.74 Table 4.1 48.2 Value σ × 1010 [m] 3.7 13.58 190.8 23 .4.8 5.40.1.00 562.6 Percent Difference 14. σ =3 3b 2πN A The table listed below was created using this equation.306 11.1.24 4.94 512.96 ⎡ J ⎤ Note: Used R = 8.56 3. Species CH4 C6H6 CH3OH σ × 1010 [m] 3. and data from Table 4.6 46. The following table was made: Species CH4 C6H6 CH3OH Tc [K ] Pc × 10 -5 [Pa ] ⎡ m3 ⎤ b × 10 5 ⎢ ⎥ ⎣ mol ⎦ 4.94 6. b= RTc 8 Pc Critical point data can be found in Table A.16 The van der Waals b parameter can be calculated using Equation 4.314 ⎢ for calculation of a.

314 ⎢ for calculation of a.9464 3σ 3 3aσ 3 ∴ C6 = 2 2πN a The σ values can be found in Table 4.00 562. ⎣ mol ⋅ K ⎥ ⎦ The equation from page 187 can be used to find C6.1.3 5.6 46.96 ⎡ J ⎤ Note: Used R = 8. 24 .39.883 0. The following table can now be created Species CH4 C6H6 CH3OH σ ×1010 [m] 3.2303 1. and the corresponding percent differences were calculated.27 3.4.1 48.17 The van der Waals a parameter can be calculated using Equation 4.2.6 C 6 × 10 77 J ⋅ m 6 1.94 512. and the following table was made: Species CH4 C6H6 CH3OH Tc [K ] Pc × 10 -5 [Pa ] 190.8 5.82 [ ] To compare the values obtained from Equation 4. a= 2 C6 2πN a ⎡ J ⋅ m3 ⎤ a⎢ ⎥ 2 mol ⎢ ⎥ ⎣ ⎦ 0.1.13.66 36.6 80. The values for the above equation were taken from Table A. first calculate the potential energy with Equation 4.13: Γ≈ − 3 α iα j 2 r6 ⎛ Ii I j ⎜ ⎜ Ii + I j ⎝ ⎞ ⎟ ⎟ ⎠ Therefore C6 = ⎛ Ii I j −3 α iα j ⎜ ⎜I +I 2 j ⎝ i ⎞ ⎟ ⎟ ⎠ We obtain the following values using this equation.

0 5.66 1.36 [ ] Percent Difference 63 202 328 The values for the van der Waals a constant have the correct qualitative trends and order of magnitude. those values predicted from basic potential theory vary significantly from corresponding states. It does not take into account the structure given to the fluid through intermolecular forces.82 1.3 12. however.13 1.Species CH4 C6H6 CH3OH C 6 × 10 77 J ⋅ m 6 Page 187 Equation 4. 25 . In fact. a more careful development includes a radial distribution function. The radial distribution function depends on pressure and temperature of the fluid. The basic potential result presented in the text assumes that the species are evenly distributed throughout the volume. which describes how the molecular density of the fluid varies with r.021 36.

4.18 van der Waals:

P=

RT a − v − b v2 RT a − 1/2 v − b T v( v + b) RT a(T ) − v − b v (v + b ) + b( v − b)

Redlich-Kwong

P=

Peng-Robinson:

P=

As you may have discovered, these equations are largely empirical with no theoretical justification. They simply represent experimental data better. We can use our knowledge of intermolecular forces, however, to explain why these may work better. If we compare these equations to the van der Waals equation, we note that the first term on the right hand side of all three equation is identical; we accounted for this term as a correction for finite molecular size (or alternatively repulsive interaction due to the Pauli Exclusion Principle). This form represents a hard sphere model. The second term, that which deals with intermolecular attraction, is different in all three models. Both of the later equations include a temperature dependence in this term. We have seen that if attractive forces depend on orientation (dipole-dipole), they fall off with T as a result of the averaging process (recall discussion of Equation 4.11). Another explanation goes as follows: as T increases, the molecules move faster, reducing the effect of intermolecular forces. If we say that the potential energy between two molecules depends on the amount of time that they spend close to each other, then it would be inversely related to velocity (The faster molecules are moving, the less time they spend in the vicinity of other species). In this case, the correction term would go as V-1, where V is the molecular velocity. If we relate molecular velocity to temperature

2 1 2 mV

=3 2 kT

Therefore the correction term goes as T-1/2, as shown in the Redlich-Kwong equation. The inclusion of a "b" term in the second term may help relax van der Waal's "hard sphere" model with a more realistic potential function, i.e., something closer to a Lennard Jones potential (Figure 4.8) than the Sutherland potential (Figure 4.7) upon which the van der Waals equation is based. It makes sense that this should be included in the force correction since this is taking into account repulsive forces. One example of a more detailed explanation follows: If we look at the Redlich-Kwong equation, it says that if we have 2 species with the same attractive strength (same a -> same magnitude of van der Waals forces), the larger species will have less of an effect on P. The following sketch illustrates how 2 species could have the same van der Waals attractive forces:

26

- +

London = London + Dipole

Species 1 smaller and polar (smaller b, same a)

Species 2 larger and non-polar (larger b, same a)

In the case above, when the two species are the same distance apart, they have the same attractive force; however, the smaller species (1) can get closer before its electron cloud overlaps. Thus it has more opportunity for attractive interactions than the larger species. The Peng-Robinson equation exhibits the most complicated form in an attempt to better fit experimental data.

27

4.19 (a) Work is defined as follows

W = − ∫ PdV Substitution of the ideal gas law for P yields W = −∫ nRT dV V

**⎛ ⎛ 1 [L] ⎞ ⎡ J ⎤⎞ W = −(2.0 [mol])⎜ ⎜ 10 [L] ⎟ ⎟ ⎜ 8.314 ⎢ mol ⋅ K ⎥ ⎟ ⎟(1000 [K ])ln⎜ ⎣ ⎦⎠ ⎝ ⎠ ⎝ W = 38.29 kJ
**

(b) Instead of substituting the ideal gas law into the definition of work, the Redlich-Kwong equation is used:

W = −n ∫

v2 v1

RT a dv − 1 / 2 v − b T v (v + b)

Substituting

⎡ J ⎤ R = 8.314 ⎢ ⎣ mol ⋅ K ⎥ ⎦ T = 1000 [K ] n = 2 [mol] ⎡ J ⋅ K1/2 ⋅ m 3 ⎤ a = 14.24 ⎢ ⎥ 2 mol ⎢ ⎥ ⎣ ⎦ 3 ⎡m ⎤ b = 2.11×10 − 5 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ ⎡ m3 ⎤ v1 = 0.0005 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ 3 ⎡m ⎤ v2 = 0.005 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣

28

Clearly.35 kJ (c) Energy balance: ∆u = q + w Since the process is reversible q = T∆s and w = ∆u − T∆s To use the steam tables conveniently. the Redlich-Kwong EOS or steam tables are appropriate for this calculation.00 ⎢ s ⎥ ⎣ kg ⋅ K ⎦ ⎛ ⎛ ⎡ kJ ⎤ ⎞ ⎡ kJ ⎤ ⎡ kJ ⎤ ⎞ ⎡ kJ ⎤ ⎟ − (1000 K )⎜ 7.6 ⎢ ⎥ u ⎣ kg ⎦ ⎡ kJ ⎤ ˆ 2 = 3462.and evaluating the resulting formula gives W = 37.5 [kJ ] The answers from the three parts agree very well. 29 . 6 − 8 . The value from Part (b) is 1. ⎡ kJ ⎤ ˆ1 = 8. 101 ⎢ ⎥ ⎢ ⎥ ⎥ ⎢ kg ⋅ K ⎥ ⎟ ⎜ ⎟ ⎜ ⎟ kg kg kg ⋅ K ⎣ ⎦ ⎣ ⎦ ⎣ ⎦ ⎣ ⎦⎠ ⎝ ⎠ ⎝ ⎡ kJ ⎤ ˆ = 1040 ⎢ ⎥ w ⎣ kg ⎦ W = 37.1 % smaller than the value from Part (c). Part (a) is not as accurate as Part (b) and Part (c) because water is not an ideal vapor. we need the initial and final pressures.2 ⎢ ⎥ u ⎣ kg ⎦ Therefore.6 MPa From the steam tables: ⎡ kJ ⎤ ˆ1 = 3522.101 ⎢ s ⎥ ⎣ kg ⋅ K ⎦ ⎡ kJ ⎤ ˆ2 = 7. 2 − 3522 .00 ⎢ ˆ =⎜ w 3462 .65 MPa P2 = 15. We can calculate these with the Redlich-Kwong EOS: P 1 = 1.

.... v RT ⎝v⎠ This expression can also be expanded in pressure. From Equation 4.. 1− x Therefore... RT Substituting B and C found above..58. 1 ⎛b⎞ ⎛b⎞ = 1 + ⎜ ⎟ + ⎜ ⎟ + . ⎛b⎞ ⎝v⎠ ⎝v⎠ 1− ⎜ ⎟ ⎝v⎠ and a ⎞ ⎛ ⎜b − ⎟ 2 Pv RT ⎠ ⎛ b ⎞ ⎝ = 1+ + ⎜ ⎟ + . we know that B' = C'= B RT C − B2 2 (RT )2 where Pv = 1 + B' P + C ' P 2 + . 1 a Pv v a = − = − b RTv RT v − b RTv 1− v To put this equation in virial form. we can utilize a series expansion: 1 = 1 + x + x 2 + x 3 + . we can obtain an expression for the compressibility factor with the van der Waals equation. 30 .20 First. we get B' = b(RT ) − a and C ' = 2ab(RT ) − a 2 (RT )2 (RT )4 Therefore..4.

= 1+ ⎜ ⎜ (RT )2 ⎟ ⎜ RT (RT )4 ⎟ ⎝ ⎠ ⎝ ⎠ 31 .2⎞ ⎛ ⎛ b(RT ) − a ⎞ Pv ⎟ P + ⎜ 2ab(RT ) − a ⎟ P 2 + ....

.21 Using the virial expansion.....⎥ = + + C'⎜ RT ⎢ + 1 + B ' RT ⎢ + ⎜ RT ⎢ v + 2 + 3 ⎥ ⎟ ⎥ v ⎢ v v2 v3 ⎥ v v ⎣ v v 2 v3 ⎦ ⎣ ⎦ ⎣ ⎦ ⎝ ⎠ ⎦ ⎣ If we combine like terms on the right side and set them equal to terms on the left.⎥ ⎦ ⎣ v v 2 v3 The virial expansion in pressure is P= RT 1 + B' P + C ' P 2 + ..4. the pressure can be written as follows ⎤ ⎡1 B C P = RT ⎢ + + + . v [ ] If we substitute the first expression into the second. we find B = B' RT C = BB' RT + C ' (RT )2 Substitute the expression for B’ into the expression for C and solve for C’: C' = C−B (RT )2 and B' = B RT 32 . we obtain 2 ⎡ ⎛ ⎡1 B C ⎤ ⎞ ⎤ ⎡1 B C ⎤ RT ⎢ ⎡1 B C ⎤ ⎟ ⎥ + + .

if we plug this back into Equation 1 we can solve for the Berthelot constants in terms of the critical temperature and the critical pressure: 27 R 2Tc2 64 Pc a= and b= RTc 8Pc 33 .4.22 At the critical point we have: Pc = RTc a − 2 vc − b Tc vc (1) RTc 2a ⎛ ∂P ⎞ + ⎜ ⎟ =0=− 2 3 ⎝ ∂v ⎠Tc (vc − b ) Tc vc (2) ⎛ 2 ⎞ 2 RTc 6a ⎜∂ P⎟ − ⎜ 2 ⎟ =0= 3 4 Tc vc ⎜ ∂v ⎟ ( vc − b ) ⎠Tc ⎝ (3) If we multiply Equation 2 by 2 and Equation 3 by (v-b) and add them together: 0= 4a 3 vc − 6a(vc − b ) 4 vc this can be solved to give: vc = 3b If we plug this back into Equation 2 and solve for a. we get: a= 9 vc RTc2 8 Finally.

We find vc = 3b 27 R 2Tc3 a= 64 Pc RTc b= 8 Pc The Berthelot equation is P= RT a − v − b Tv 2 (1) (2) (3) First. substitute Equation 1 into the first term on the right-hand side and rearrange to get RT a P= b − 3vr − 1 Tv 2 Now.22). we get P= 8PcTr 27 PcTc b 2 − 3v r − 1 Tv 2 34 .4.23 Before we can find the reduced form. we need to find expressions for a and b in terms of critical point data (Problem 4. substitute Equation 3: P= 8 PcTr a − 3v r − 1 Tv 2 Substitute Equation 2: 27 R 2Tc3 64 Pc Tv 2 P= 8 PcTr − 3v r − 1 From Equation 3: R 2Tc2 = 64 Pc2 b 2 Substituting this result.

Finally. substitute Equation 1: P= 2 8PcTr 3PcTc vc − 3v r − 1 Tv 2 This can be rewritten as Pr = 8Tr 3 − 2 3vr − 1 Tr vr 35 .

5 MPa (15 bar) we see that the plot reaches a constant value of around -118 cm3/mol. We may choose to report this value as B.24 (a) The virial equation is: z= Pv D B C = 1 + + 2 + 3 +. B. we should get a straight line at low to moderate pressures with an intercept equal to the second virial coefficient. and a slope equal to the third virial coefficient. RT v v v (1) We can rewrite this equation: (z − 1)v = ⎝ C ⎛ Pv ⎞ − 1⎠ v = B + +. If we plot (z-1)v vs. as shown on the next page. C. RT v (2) PvT data from the steam tables are given in the steam tables and corresponding values of (z-1)v and 1/v can be calculated.5 2 1/v (mol/l ) We see that at pressures above 1. At very low pressures.5 1. the curve is indeed linear and gives an intercept of -140 cm3/mol.. 1/v for T = 300 oC is shown below. 1/v. Plot to determine the second virial coeff at 300 C -115 -120 (z -1)v (cm3 / mol) -125 (z -1)v -130 -135 0 1 0.. A more careful examination of Equation 2 suggests another possibility. An illustrative plot of (z-1)v vs.. Can you calculate C? 36 . The slope of this region would yield the third virial coefficient. C.4..

What value would you be more apt to use? Water exhibits this “odd” general behavior at all temperatures. 900.5 2 1/v (mol/l ) If we do this at other values of T. temperature and get an idea of the differences in the two approaches. Note that the average value is indicative of the 1st method above while the value at the lowest pressure used is indicative of the second value used. 800.The first value uses much more data while the second method uses limited data in a better range. 500. 400. Temperatures of 200.373 -125 (z -1)v -130 lin -135 0 1 0.058x . and 1200 oC analyzed in this manner. 250.5 1. The results are reported in the table and figure below. Plot to determine the second virial coeff at 300 C -115 -120 (z -1)v (cm3 / mol) y = 177.140. 1000. 600. 700. 300. we can compile a set of second virial coefficients vs. T 200 250 300 350 400 500 600 700 800 900 1000 1200 B (Level) -214 -156 -118 -89 -72 -49 -34 -24 -17 -13 -9 -3 B (Linear) -226 -173 -140 -102 -103 -83 -73 -68 -66 -51 -50 -51 B (AVG) -215 -157 -120 -92 -76 -54 -39 -30 -24 -19 -16 -11 B(1st value) -220 -168 -134 -99 -95 -75 -63 -57 -54 -52 -52 -52 37 . Also reported were the average value and the value at the lowest pressure used. 350.

values of -142.2 cm3/mol and -7160 cm6/mol2 are reported for B and C. Dymond and E. (b) There are several alternatives how to solve this problem.H. respectively.⎥ v2 ⎦ ⎣v Take the derivative: ⎤ ⎡ 1 2 BH 2 O ⎥ ⎛ ∂P ⎞ ⎢ ⎜ ⎟ = 0 = RTc − 2 − ⎥ ⎢ v ⎝ ∂v ⎠Tc v3 c ⎦ ⎣ c so ⎡ cm3 ⎤ v BH 2O = − c = −28 ⎢ ⎥ 2 mol ⎢ ⎥ ⎣ ⎦ 1 J. A Critical Compilation. 1980.Second Virial Coefficient of Water by 4 Methods 0 -50 B (water) cm 3 /mol -100 B (average) -150 B (lowest P) B (Level) -200 B (Linear) CRC -250 1000 1250 1500 250 500 750 T (K) For comparison.. at 260 oC1.. They agree most closely with the first (level) method. 38 .B. Oxford University Press. Values of B reported in the CRC are also shown on the summary plot. Oxford. The Virial Coefficients of Pure Gases and Mixtures. Smith. each of which comes up with a slightly different result: Alternative 1: Rewrite the virial equation: ⎤ ⎡ 1 BH 2 O P = RT ⎢ + + .

Alternative 2: From the virial equation: ⎡ cm3 ⎤ ⎛ Pc vc ⎞ ⎟ = − − 1 43 . 2 BH 2 O = ⎜ v ⎢ ⎥ ⎜ RT ⎟ c mol ⎢ ⎥ ⎝ c ⎠ ⎣ ⎦ Alternative 3: ⎤ ⎡ 1 BH 2 O C H 2 O P = RT ⎢ + + + ...⎥ v2 v3 ⎦ ⎣v so ⎤ ⎡ 1 2 BH 2O 3C H 2O ⎥ ⎛ ∂P ⎞ ⎢ − ⎜ ⎟ = 0 = RTc − 2 − 3 ⎥ ⎢ v ⎝ ∂v ⎠Tc v v4 c c ⎦ ⎣ c (1) and ⎡ ⎛ ∂2P ⎞ 6B 12C H 2O ⎤ ⎥ ⎜ ⎟ = 0 = RTc ⎢ 2 + H 2O + 4 5 ⎜ ∂v 2 ⎟ ⎢ v3 vc vc ⎥ ⎝ ⎠Tc ⎦ ⎣ c (2) Multiply Equation 1 by (4/vc) and add to Equation 2 to get: − 2 v3 c − 2 BH 2 O v4 c =0 so ⎡ cm3 ⎤ BH 2O = −vc = −56 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ 39 .

repeat the process until they are. 000551 = 0 .314 ⎢ mol ⋅ K ⎥ ⎟ mol ⎢ ⎥ ⎣ ⎦ ⎠ ⎣ ⎦ 6 × 105 [Pa ] = ⎝ − ⎡ m3 ⎤ ⎛ ⎡ m3 ⎤ ⎞ v − 0. Guess P sat : P sat = 6 [bar ] 2.00459 ⎡⎛ ⎤ ⎞ a ⎜ RT − ⎟ − P sat ⎥dv = 1325. If the values of the expressions are not equal. The general method is as follows 1. 851 ⎢ ⎥ ⎜ 2 ⎟(363.000152 ⎢ v v ⎢ ⎢ ⎥ high ⎥ mid ⎥ ⎢ mol ⎦ ⎢ mol ⎦ ⎥ ⎥ ⎢ mol ⎦ ⎥ ⎣ ⎣ ⎣ 3. Find areas under the curves with the following expressions v mid ∫ [P sat − f (v ) dv ] v low v high v mid ∫ [ f (v ) − P sat ]dv [ f (v ) represents the particular EOS implicit in molar volume being used. Guess P sat 2.78 ⎢ ∫ ⎜ v − b T 1 / 2 v (v + b ) ⎟ ⎥ ⎠ ⎣⎝ ⎦ 0. vhigh 3.0001 ⎢ ⎥⎟ ⎜ ⎟ mol ⎢ ⎥ ⎢ ⎣ ⎦ ⎣ mol ⎥ ⎦⎠ ⎝ ⎡ m3 ⎤ ⎡ m3 ⎤ ⎡ m3 ⎤ = 0 .19 P − ⎢ ∫ ⎢ ⎜ v − b T 1 / 2 v (v + b ) ⎟ ⎥ ⎝ ⎠⎦ 0.] 4.000551 ⎡ 40 . 00459 vlow = 0.000551 ⎢ 0. ⎞⎤ a sat ⎛ ⎜ RT − ⎟⎥dv = 1157. Calculate values of molar volumes that result at the chosen P sat : vlow .4. vmid .25 A trial-and-error is the easiest method for solving this problem.000152 ⎣ 0. (a) 1.15 [K ]) ⎜ 8. Calculate molar volume solutions for: RT a − P sat = 1 / 2 v − b T v (v + b ) ⎡ J ⋅ K1/2 ⋅ m 3 ⎤ ⎛ ⎡ J ⎤⎞ 41 .15 K )1 / 2 v⎜ ⎥ v + 0.0001 ⎢ (363.

000551 = 0 . Repeat this process until the areas are equal.4.7 bar. Repeat this process until the areas are equal.066 ⎢ .000152 ⎢ v v ⎢ ⎢ ⎥ high ⎥ mid ⎥ ⎢ ⎢ ⎢ ⎣ mol ⎥ ⎦ ⎣ mol ⎥ ⎣ mol ⎥ ⎦ ⎦ 3.00459 ∫ 4.48 ⎦ 0. The Peng-Robinson EOS results in a value that is 13. ⎡ sat ⎤ RT aα (T ) ⎢ P − v − b − v(v + b) + b(v − b ) ⎥dv = 1568.000551 ⎣ 0.000152 ⎣ 0.945 [bar ] The value calculated with the Redlich-Kwong EOS is 11. α (T ) = 1.9% greater than the measured value of 5.188 2 mol mol ⎢ ⎥ ⎢ ⎥ ⎣ ⎦ ⎣ ⎦ ⎡ m3 ⎤ ⎡ m3 ⎤ ⎡ m3 ⎤ = 0 .25% less than the measured value. 41 . Guess Psat : Psat = 6 [bar ] 2.000551 RT aα (T ) − v − b v(v + b) + b(v − b ) ∫ ⎡ RT aα (T ) sat ⎤ ⎢ v − b − v(v + b) + b(v − b ) − P ⎥dv = 1100. 00459 vlow = 0.38 [bar ] (b) 1. This occurs approximately at P sat = 6. Calculate molar volume solutions for P sat = using ⎡ m3 ⎤ ⎡ J ⋅ m3 ⎤ a = 2. b = 9 × 10 − 6 ⎢ ⎥ ⎥ . This occurs approximately at P sat = 4.19 ⎦ 0.

⎡⎛ ⎤ ⎡ J ⎤⎞ 0.15 K ⎞⎤ ⎟⎥ ⎜1 − ⎟ ⎜ 3 05.84 × 105 [Pa ] 2 a= ⎡ J ⋅ m3 ⎤ = 0.54226(0.099)2 ⎢ ⎣ α (T ) = 1. and α (T ) . calculate a .12 ( ) ⎛ 243.84 × 10 [Pa ] ⎡ α (T ) = ⎢1 + 0.26992(0.167 ×10 ⎢ ⎣ mol ⎥ ⎦ ⎡ m3 ⎤ ⎡ 3⎤ −3 m = × . we can find the three solutions to the Peng-Robinson EOS: P sat = RT aα (T ) − v − b v(v + b) + b(v − b ) Using the values calculated above and P sat = 10.099 Now we can calculate the required parameters.1.314 ⎢ ⎣ mol ⋅ K ⎥ ⎦ we get ⎡ m3 ⎤ −4 v = 7.45724⎢⎜ ⎟(305. v = 2.4 [K ]) ⎜ 8.4 K ⎥ ⎠⎦ ⎝ 2 Now.6036 ⎢ ⎥ 2 ⎢ mol ⎦ ⎥ ⎣ ⎡ m3 ⎤ ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ ⎛ ⎡ J ⎤⎞ 0.26 First.84 [Pa ] w = 0.1: Tc = 305.37464 + 1. 42 .045 × 10 − 5 b= 5 48. Therefore.314 ⎢ mol ⋅ K ⎥ ⎟ ⎣ ⎦⎠ ⎝ = 4.199 × 10 − 5 ⎢ ⎥ .099) − 0.4 [K ])⎥ ⎜ 8. v 1 . b .4 [K ] Pc = 48.6 × 105 [Pa ] ⎡ J ⎤ R = 8. while the molar volume of saturated ethane vapor is the largest value. 578 10 ⎢ ⎢ ⎥ ⎥ ⎢ ⎢ ⎣ mol ⎥ ⎣ mol ⎥ ⎦ ⎦ The molar volume of saturated ethane liquid is the smallest value from the list above. From Table A.4.07780⎜ ⎟(305.314 ⎢ mol ⋅ K ⎥ ⎟ ⎣ ⎦⎠ ⎣⎝ ⎦ 48.

199 × 10 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ ⎡ g ⎤ 36.7% greater.578 ×10 ⎢ ⎥ ⎢ ⎣ mol ⎥ ⎦ Both of the densities calculated with the Peng-Robinson EOS are larger than the reported values. 43 .05% larger. and the vapor density is 18.0694 ⎢ 3 ⎞ (MW )ethane ⎣ mol ⎥ ⎦ ⎛ ⎜ 1m ⎟ = 0.0694 ⎢ 3 ⎞ (MW )ethane ⎣ mol ⎥ ⎦ ⎛ ⎜ 1m ⎟ = 0.501 ⎡ g ⎤ = ρ liq = ⎢ 3⎥ liq 3 3 ⎜ ⎡ 3 ⎤ ⎝ (100 ) cm ⎟ v ⎣ cm ⎦ ⎠ −5 m 7.⎡ g ⎤ 36.0229 ⎡ g ⎤ = ρ vap = ⎢ 3⎥ ⎡ 3 ⎤⎜ v vap (100)3 cm3 ⎟ ⎣ cm ⎦ ⎝ ⎠ −3 m 1. The liquid density is 7.

08664 RTc = 2.97 ×10 − 4 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ Now calculate the total volume of gas in the 30.69 × 10 − 5 b= Pc Now use the EOS to find the molar volume: P= RT a − 1 / 2 v − b T v(v + b ) Assume the temperature of the gas is 22 ºC.42748R 2Tc2.1.1 / kg ) 1.4.97 × 10 − 4 ⎢ ⎥ ⎢ ⎦ ⎣ mol ⎥ and the mass m = 6. substitute values.) 0.116.29 × 10 6 liters = 1290 m 3 Therefore. calculate the value of the gas: Value = ($6.5 = 1.1.000 units: Vtotal = (30000 units )(43 [liter/unit ]) = 1. First.83 × 105 kg Now.300 ( ) ( ) 44 .56 ⎢ ⎥ 2 Pc mol ⎢ ⎥ ⎣ ⎦ ⎡ m3 ⎤ ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ (Note: Critical data for nitrogen obtained in Table A. calculate the a and b parameters: a= ⎡ J ⋅ m 3 ⋅ K1 / 2 ⎤ 0.02801 kg/mol) = 1.55 × 10 6 mol (0. and find the molar volume with a solver function: ⎡ m3 ⎤ v = 1.27 (a) We will use the Redlich-Kwong EOS in order to obtain an accurate estimate.55 × 10 6 mol 3 ⎡m ⎤ 1. the number of moles is: n= 1290 m 3 = 6.83 × 105 kg = $1.

and find the molar volume with a solver function: ⎡ m3 ⎤ v = 1. (b) First.314 ⎢ ⎟ ⎜ ⎟(295 K ) ⎜ RT ⎝ ⎣ mol ⋅ K ⎥ ⎦⎠ = 1.) b= 0. substitute values. calculate the a and b parameters: ⎡ m3 ⎤ ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ ⎡ J ⋅ m 3 ⋅ K1 / 2 ⎤ 0.If we use the ideal gas law.113. we find: ⎛ ⎡ J ⎤⎞ 8. we find that Value = $2.428.98 × 10 − 4 = v= P 12400000 Pa Following the steps above.000 45 .265. we find ⎡ m3 ⎤ v = 1.64 × 10− 4 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ which provides Value = $2.08664 RTc = 2.1. Value = $1.21 × 10 − 5 Pc Assume the temperature of the gas is 22 ºC.1.42748R 2Tc2.200 The value calculated using the ideal gas law is $3100 less than the value calculated using the Redlich-Kwong EOS.000 With the ideal gas law.74 ⎢ a= ⎥ Pc mol 2 ⎢ ⎥ ⎣ ⎦ ⎡ m3 ⎤ ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ (Note: Critical data for oxygen obtained in Table A.53 × 10− 4 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ Following the steps presented in Part (a).5 = 1.

The value found with the ideal gas law is $163. 46 .000 less than the value found using the RedlichKwong EOS.

4. 5 0. find an expression for a: ⎛ 2 RTC 2⎞ 0.5 or at the critical point v3 − ⎞ RTc 2 ⎛ RT a ab v +⎜ − c b − b 2 ⎟v − =0 0 .28 First.5 a=⎜ ⎜ 3vc + P + b ⎟ ⎟ Pc Tc C ⎝ ⎠ Substitute the above expression into Equation 3 to get 2 3 b 3 + 3vc b 2 + 3vc b − vc =0 The one real root to this equation is b = 21 / 3 − 1 vc Substitute Equation 4 into Equation 1: ( ) (4) 47 .5 ⎜ ⎟ Pc P P T P T c c c ⎝ c c ⎠ Now expand (v − vc )3 = 0 2 3 v 3 − 3v 2 vc + 3vvc − vc =0 Setting the coefficients equal we get the following expressions. v3 − RT 2 ⎛ a RT ab ⎞ v +⎜ − b − b 2 ⎟v − =0 P P ⎝ PT 1 / 2 ⎠ PT 0. rewrite the Redlich-Kwong equation in cubic form. 3vc = 2 3vc = 3 vc = RTc Pc a PcTc0.5 ab − RTc b − b2 Pc (1) (2) (3) Pc Tc0.5 Using Equation 2.

48 R 2Tc2 = Pc2 b 2 (0.2599 T vvc (v r + 0. substitute Equation 1 and Equation 4.b= 0.42748RTc2.2599 ) Now.5 Pc (Equation 4. 5 v r − 0.2599) From Equation 4.48 into the expression for a to get a= 0.2599 PC T 0.2599 ) Replacing a with Equation 4.48) Now.48 P= 3Tr Pc a − 0 .08664 RTc Pc (Equation 4.50) The Redlich-Kwong equation is P= RT a − v − b T 0.5v(v + b ) We can use Equation 4 to get 0.5vvc (vr + 0.42748R 2Tc2.47) Pv To verify Equation 4.5 vvc (v r + 0.2599 T 0.50. substitute Equation 4.47 yields P= 3Tr Pc 0.5 − v r − 0.08664)2 48 . substitute Equation 1 into z c = c c RTc ⎛ RTc Pc ⎜ ⎜ 3P c zc = ⎝ RTc ⎞ ⎟ ⎟ 1 ⎠= 3 (Equation 4.2599 RT a b P= − vr − 0.

08664 )2 Tr0.2599) (0.2599 Tr0.2599) Now.2599) (Equation 4. Pr = 3Tr 1 − 0 .2599 )2 − v r − 0.which upon substitution yields P= 3Tr Pc Pc b 2 0.2599Tr vr (vr + 0. 5 vr − 0.42748 − v r − 0.5 v r (v r + 0.49) 49 .5 vvc (v r + 0.2599 0.2599 (0.08664)2 Therefore.42748 ⋅ (0. use Equation 4: P= 3Tr Pc Pc 0.

001001 ⎢ ⎥ ⎢ ⎥⎥ −1 ⎛ kg kg ⎡ m3 ⎤ ⎞ ⎢ ⎢ ⎥ ⎢ ⎥ ⎣ ⎦ ⎣ ⎦⎥ β (20 º C ) = ⎜ 0.001044 ⎢ ⎥ ⎟ ⎢ ⎥ ⎟ ⎜ 10 K ⎢ ⎥ ⎦⎠ ⎢ ⎣ kg ⎥ ⎝ ⎥ ⎢ ⎦ ⎣ β (20 º C ) = 2. we can base all our calculations on saturated liquid water since the molar volume of liquids are weakly dependent on pressure.001047 ⎢ ⎛ kg ⎦ kg ⎦ ⎡ m3 ⎤ ⎞ ⎢ ⎢ ⎥ ⎢ ⎥⎥ ⎣ ⎣ β (100 º C ) = ⎜ 0. we can calculate the thermal expansion coefficients ⎡ ⎡ m3 ⎤ ⎡ m3 ⎤ ⎤ − ⎢ 0 . Therefore. a similar approximation will be used.0 × 10 − 4 K -1 −4 [ ] β (100 º C ) = 6.001003 ⎢ v ⎥ kg ⎢ ⎥ ⎣ ⎦ ⎡ m3 ⎤ ˆ sat (95 º C ) = 0.001047 ⎢ v ⎥ kg ⎢ ⎥ ⎣ ⎦ Using these values.001002 ⎢ v ⎥ ⎢ kg ⎦ ⎥ ⎣ ⎡ m3 ⎤ ˆ sat (25 º C ) = 0. our results are also applicable to sub-cooled water (the pressure is greater than the saturation pressure). To find the thermal expansion coefficient.71 × 10 [K ] -1 The accuracy of these values may be limited since they are based on the small differences between liquid volumes. 001003 0 . From the steam tables β= 1 ⎡ m3 ⎤ ˆ sat (15 º C ) = 0. To calculate the isothermal compressibility.001044 ⎢ v ⎥ ⎢ kg ⎦ ⎥ ⎣ ⎡ m3 ⎤ ˆ sat (105 º C ) = 0.001001 ⎢ v ⎥ kg ⎢ ⎥ ⎣ ⎦ 3 ⎡m ⎤ ˆ sat (20 º C ) = 0.001040 ⎢ ⎥⎥ −1 ⎢ 0.4.29 Since we are concerned with liquid water. we will use the following approximation ⎡v ˆ sat (T + 5 º C ) − v ˆ sat (T − º C ) ⎤ ˆ sat (T + 5 º C ) − v ˆ sat (T − º C ) ⎤ 1 ⎡v = ⎢ ⎥ ⎢ ⎥ sat ( ) ( ) T T 5 º C 5 º C + − − 10 K ˆ sat (T ) ⎢ ˆ ( ) v v T ⎥ ⎢ ⎥ ⎣ ⎦ ⎣ ⎦ This approximation is valid even though the saturation pressure changes because molar volume is weakly dependent on pressure.001040 ⎢ v ⎥ kg ⎢ ⎥ ⎣ ⎦ 3 ⎡m ⎤ ˆ sat (100 º C ) = 0. It is 50 .001002 ⎢ ⎥ ⎟ ⎢ ⎥ ⎜ ⎟ 10 K ⎢ ⎥ ⎣ kg ⎥ ⎦⎠ ⎢ ⎝ ⎢ ⎥ ⎣ ⎦ ⎡ ⎡ m3 ⎤ ⎡ m3 ⎤ ⎤ ⎥ − 0.

001010 0.99 × 10 −10 ⎢ ⎥ ⎥ ⎣ Pa ⎦ ⎣ MPa ⎦ −1 ⎛ ⎡ m3 ⎤ ⎞ κ (100 º C ) = ⎜ 0.001000 0.79 ×10 −10 ⎢ ⎥ κ (100 º C ) = 4. Specific Volume of Liquid Water vs.001044 ⎢ ⎥ ⎟ ⎜ ⎟ ⎢ ⎣ kg ⎥ ⎦⎠ ⎝ ⎡ m3 ⎤ ⎞ ⎢ ⎥⎟ ⎟ ⋅ kg MPa ⎢ ⎥ ⎣ ⎦⎠ ⎡ 1 ⎤ ⎡1⎤ = 4.9949 3 T = 20ºC T = 100 ºC Linear (T = 100 ºC) Linear (T = 20ºC) v = -5E-07*P + 0.001002 ⎢ ⎥ ⎟ ⎜ ⎢ kg ⎦ ⎥⎟ ⎣ ⎝ ⎠ −1 ⎛ ⎜ 5 × 10 − 7 ⎜ ⎝ ⎡ m3 ⎤ ⎞ ⎢ ⎥⎟ ⋅ kg MPa ⎢ ⎥⎟ ⎣ ⎦ ⎠ κ (20 º C ) = 4.000990 0 5 v = -5E-07*P + 0.001044 R2 = 0.001030 0.001050 Specific Volume [m /kg] 0.001002 R2 = 0.79 ×10 − 4 ⎢ ⎥ ⎣ MPa ⎦ ⎣ Pa ⎦ ⎛ ⎜ 5 ×10 − 7 ⎜ ⎝ 51 .99 × 10 − 4 ⎢ ⎡ 1 ⎤ ⎡1⎤ = 4. ⎛ ⎡ m3 ⎤ ⎞ κ (20 º C ) = ⎜ 0.001020 0.001040 0. Pressure 0.9979 10 15 20 25 Pressure [MPa] It is clear that sat ⎛ dv ⎜ ˆ ⎜ dP ⎝ ⎞ ⎛ dv ˆ sat ⎞ ⎟ ⎟ =⎜ = 5 × 10 − 7 ⎟ ⎜ dP ⎟ ⎠T = 20 0 º C ⎝ ⎠T =100 0 º C ⎡ m3 ⎤ ⎥ ⎢ ⎥ ⎢ kg ⋅ MPa ⎦ ⎣ Therefore.κ= sat ⎛ dv ⎜ ˆ ˆ sat (T ) ⎜ v ⎝ dP −1 ⎞ ⎟ ⎟ ⎠T The derivatives are determined from the following graph.

30 (a) Substitute critical data into the Rackett equation: vcalc = 46 × 10 ⎡ cm 3 ⎤ vcalc = 38 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ Now. while ethane and methane had the smallest percent errors.5% ⎡ cm 3 ⎤ vcalc = 68.2 ⎢ ⎥ ⎢ ⎣ mol ⎥ ⎦ (d) Error = 10.5 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ Error = 19.1% ⎡ cm 3 ⎤ vcalc = 161.4.5 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ (e) Error = 13. calculate the error.08775(0. The alkenes have low percentile errors due to their nonpolar nature.6) [0.314)(190. (8.7% 1-hexanol had the largest percent error.8% ⎡ cm 3 ⎤ vcalc = 20.29056 − 0.2 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ (c) Error = 1. 52 .8% ⎤ ⎞ ⎟ × 100⎥ % ⎟ ⎥ ⎠ ⎦ (b) ⎡ cm 3 ⎤ vcalc = 54.008)][1+ (1−111 / 190 ) ] 5 2/7 ⎡⎛ v calc − vexp Error = ⎢⎜ ⎢⎜ vexp ⎣⎝ Error = 0. which the alcohols and acids had large percentile errors due to being polar substances and exhibiting hydrogen bonds.

the required quantities can be found.8393 Therefore.8376 + (0.616 Pr = Pc 48.48. ⎡ J ⋅ m 3 ⋅ K1 / 2 ⎤ a = 9.15 [K ] T = = 1.1.1. we can make use of the generalized compressibility charts.31 (a) Since we are given the temperature and pressure.1.12 305.099 By double interpolation of the charts z (0 ) = 0. Room temperature was assumed to be 25 ºC.1 and Equations 4.518 × 10 − 5 n ⎛ ⎞ 40 [kg ] ⎜ ⎜ 0.15 [K ]) ⎟ ⎣ mol ⋅ K ⎥ ⎦⎠ ⎝ 0.796 m 3 [ ] ( [ ]) [30 ×10 5 [Pa ]] (b) The Redlich-Kwong EOS should give reasonably accurate results. Using data from Table A.8376 z (1) = 0.74 [bar ] w = 0. The molar volume is required for the calculations. so v =V = V 0.0168 and z = z (0 ) + wz (1) = 0. ⎜ (0.4. Tr = 343.4 [K ] Tc 30 [bar ] P = = 0.03007 [kg/mol] ⎠⎝ V= znRT = P V = 0.314 ⎢ ⎜ ⎟(343.099 )(0.1 m 3 = = 7.47 and 4.03007 [kg/mol] ⎟ ⎟ ⎝ ⎠ ⎡ m3 ⎤ ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ Using data from Table A.88 ⎢ ⎥ 2 ⎢ mol ⎥ ⎣ ⎦ 53 .8393)⎛ ⎜ ⎞⎛ 30 [kg ] ⎡ J ⎤⎞ ⎟ ⎜ ⎟ 8.0168) = 0.

3 [bar ] 54 .⎡ 3⎤ −5 m = × b 4.51 10 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ Substituting these values into the Redlich-Kwong EOS and evaluating gives P = 191.

28 × 10 − 5 Pc ⎡ m3 ⎤ ⎥ ⎢ ⎥ ⎢ mol ⎦ ⎣ (Note: Critical data for propane obtained in Table A.000109 ⎢ ⎥ ⎢ ⎦ ⎣ mol ⎥ ∴V = 0. e.1. the solver function on a graphing calculator ⎡ m3 ⎤ v = 0.124 m 3 [ ] 55 .1.15 K ) ⎣ mol ⋅ K ⎥ ⎦⎠ V = nRT = P V = 0.5 = 18.4.42748R 2Tc2.0441 ⎢ ⎣ mol ⎥ ⎦ ⎣ mol ⎦ Now calculate the volume: ⎡ (1130 [mol])⎛ ⎜ ⎜ 8.33 ⎢ ⎥ 2 Pc mol ⎥ ⎢ ⎦ ⎣ 0.08664 RTc = 6.870 m 3 [ ] 35 × 105 [Pa ] (b) The Redlich-Kwong EOS is P= where a= b= RT a − v − b T 1 / 2 v(v + b ) ⎡ J ⋅ m 3 ⋅ K1 / 2 ⎤ 0.g..314 ⎢ ⎝ J ⎤⎞ ⎟ ⎟(50 + 273. there is only one unknown in the Redlich-Kwong EOS: v .0441 ⎡ ⎢ ⎥ ∴n = 50 [kg ] = 1130 [mol] ⎡ kg ⎤ 0. Using a numerical technique.) Now that these values are known.32 (a) For propane kg ⎤ (MW ) propane = 0.

64 × 10 − 5 Pc Now every variable in the Peng-Robinson EOS is known.873 T = 370 K Tc )]2 α = 1. 56 .052 Therefore.605 ⎡ J ⋅ m3 ⎤ 0.26992(0.825 Pr = Pc 42. ⎡ m3 ⎤ v = 0.44 bar By double-interpolation on the compressibility charts (Appendix C).873 370 K Tc 35 bar P = = 0.37464 + 1.02 ⎢ ⎥ Pc mol ⎥ ⎢ ⎦ ⎣ ⎡ m3 ⎤ ⎥ ⎢ ⎥ ⎢ mol ⎦ ⎣ 0.15) K = 0.1152)2 = 0.54226(0.107 m 3 [ ] (d) We must calculate the reduce temperature and pressure to use the compressibility charts: Tr = 323.1349 z (1) = −0.07780 RTc b= = 5.15 K T = = 0.(c) The Peng-Robinson EOS is P= where RT aα (T ) − v − b v(v + b ) + b(v − b ) α = 1 + κ 1 − Tr Tr = [ ( (50 + 273. z (0 ) = 0.0000942 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ ∴V = 0. except v.45724(RTc )2 = 1.152) − 0.081 a= κ = 0.

00009749 ⎢ v= ⎥ P ⎢ mol ⎦ ⎥ ⎣ V = 0.110 m 3 [ ] 57 .Pv = z = z (0 ) + wz (0 ) = 0. ⎡ m3 ⎤ v = 0.107 m 3 [ ] Using the generalized compressibility charts: ⎡ m3 ⎤ v = 0.152(− 0.1349 + 0.052) = 0.111 m 3 (e) From ThermoSolver Using the Peng-Robinson equation.127 RT ⎡ m3 ⎤ 0.127 RT = 0.0000971 ⎢ ⎥ ⎢ ⎦ ⎣ mol ⎥ Therefore. V = 0.00009429 ⎢ ⎥ mol ⎥ ⎢ ⎦ ⎣ ∴V = 0.

33 Note: Multiple possibilities exist for which substance to use in the vial.45724 ⎡ J ⋅ m3 ⎤ = 0. the molar volume at that state is constrained by the critical temperature and pressure. and it is safe to use.18 × 10 − 4 ⎢ 118 = ⎥ ⎢ ⎥ ⎢ ⎢ ⎦ ⎣ mol ⎥ ⎦ ⎣ mol ⎥ Now.4 × 10 − 4 5 73.07780 = 3.1 º C Clearly.2 K = 31.314 ⎢ mol ⋅ K ⎥ ⎟ ⎟ (304.76 bar (the critical pressure of carbon dioxide). CO2 is a suitable substance.847 mol vc ⎡ cm 3 ⎤ 118 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ [ ] 58 . the vial must withstand 73. we can use the PengRobinson EOS.1. The solution using one possibility is illustrated below.76 × 10 [Pa ] α =1 ⎡ m3 ⎤ ⎥ ⎢ mol ⎥ ⎢ ⎦ ⎣ Substitute the above parameters and solve for the molar volume: ⎡ cm 3 ⎤ ⎡ m3 ⎤ vc = 1. n= 100 cm 3 V = = 0.2 K ) ⎦⎠ ⎣ ⎝ b = 0.76 × 10 5 [Pa ] 2 a = 0.4. we that for carbon dioxide Tc = 304. To estimate the molar volume.40 ⎢ ⎥ ⎢ mol 2 ⎦ ⎥ ⎣ ⎛ ⎡ J ⎤⎞ ⎜ ⎜ 8.2 K ) ⎣ ⎦⎠ ⎝ 73. (c) Since the substance passes through its critical point. Calculate the necessary parameters for the EOS: ⎛ ⎡ J ⎤⎞ 2 ⎜ ⎜ 8. From the Appendix A. Therefore. (a) The substance must have a critical temperature above room temperature but below the temperature of one’s hand.314 ⎢ mol ⋅ K ⎥ ⎟ ⎟(304. we can calculate the required amount of CO2.2. (b) The vial must be able to withstand the pressure of the substance at its critical point.

P critical point liquid part c part d not enough CO2 liquid .(d) If the vial contains less substance than needed. Then.vapor vapor v 59 . the substance will not pass through the critical point. As the substance is heated. it will go through a transition from a saturated liquid and vapor mixture to superheated vapor. Therefore. it will become a supercritical fluid once the critical temperature is exceeded. the molar volume will be greater.

66 [K ]) ⎦⎠ ⎣ ⎝ 5 ( ) From the compressibility charts.0897 Therefore.008)0. z = z (0 ) + wz (1) = 0.25 ⎢ ⎥ mol Pc ⎢ ⎥ ⎣ ⎦ 0.68 × 10 − 5 Pc ⎡ m3 ⎤ ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ T = Tr Tc = 209.07780 RTc = 2. z (0 ) = 0.4. ⎛ ⎡ 3 ⎤⎞ −4 m ⎜ 55.0897 z = 0. P= RT aα (T ) − v − b v(v + b ) + b(v − b ) −4 v = 1.2 × 10 5 [Pa ] The molar volume is the only unknown in the following equation. α (T ) = 1 + κ 1 − Tr α (T ) = 0.9626 a= b= [ ( )]2 ⎡ J ⋅ m3 ⎤ 0.45724(RTc )2 = 0.2 × 10 [Pa ] 1.5984 + (0.66 [K ] P = Pr Pc = 55.83 × 10 ⎡ m3 ⎤ ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ Therefore.5984 z (1) = 0.34 Methane: The following quantities are required to calculate the molar volume with the Peng-Robinson equation.599 60 .314 ⎢ mol ⋅ K ⎥ ⎟ ⎟(209.83 × 10 ⎢ ⎥⎟ ⎜ mol ⎢ ⎥⎟ ⎣ ⎦ ⎝ ⎠ = 0.58 z= ⎛ ⎞ J ⎤ ⎡ ⎜ ⎜ 8.

599 (Compressibility charts) The value from the Peng-Robinson EOS is 3. Methanol z = 0.2% smaller than the value from the charts.5984 + (0.559 Therefore.1.14 ×10 − 4 ⎢ ⎥ ⎢ ⎣ mol ⎥ ⎦ ∴ z = 0. 61 .559 )0. the Peng-Robinson equation produces ⎡ m3 ⎤ v = 3.0897 From Table A.Methanol: Following the procedure outlined above.31% smaller than the value from the charts.651 (Peng-Robinson) z = 0.1. w = 0.649 (Compressibility charts) The value from the Peng-Robinson EOS is 0.649 Summary: Methane z = 0.5984 z (1) = 0.0897 z = 0.58 (Peng-Robinson) z = 0.651 Using the compressibility charts: z (0 ) = 0. z = z (0 ) + wz (1) = 0.

The pressure is greater than the critical pressure. so the ammonia is a liquid.718 Pr = Pc 112.1.35 From Table A.1351 Therefore.77 bar z (0 ) = 0.76 × 10 − 5 P ⎡ m3 ⎤ ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ Since the temperature of the ammonia in this system is below the critical temperature.15) K = 0.1: Tc = 405.38RT = 3.4.25 Calculate reduced temperature and pressure: Tr = (92 + 273. we know the ammonia is not a supercritical fluid.6 K Pc = 112.4133 From interpolation of the compressibility charts: z (1) = −0.77 bar w = 0.38 RT and v= 0. 62 .5 bar P = = 2.6 K Tc 306. Pv = z = z (0 ) + wz (1) = 0.9 T = 405.

08664 RTc Pc Substituting critical data from Table A.03 ⎢ ⎥ 2 ⎢ ⎥ ⎣ mol ⎦ ⎡ J ⋅ K1/2 ⋅ m 3 ⎤ abut = 29.2 [mol] Therefore. we can use mixing rules to calculate the parameters for the mixture.123 ×10 -3 ⎡ kg ⎤ ⎢ ⎦ ⎣ mol ⎥ ⎡ kg ⎤ ⎢ ⎣ mol ⎥ ⎦ = 1152.4. First.2 [mol] = 860.72 ⎢ ⎥ 2 ⎢ mol ⎥ ⎣ ⎦ 63 .1 gives ⎡ J ⋅ K1/2 ⋅ m3 ⎤ aace = 8.62 ×10 − 5 ⎢ ⎥ ⎢ ⎦ ⎣ mol ⎥ ⎡ m3 ⎤ bbut = 8.87 ⎢ ⎥ 2 mol ⎢ ⎥ ⎣ ⎦ 1/2 3 ⎡J ⋅K ⋅m ⎤ ∴ amix = 14.07 (1 − 0.36 Let the subscript “ace” represent acetylene and “but” represent n-butane.07 ⎢ ⎥ 2 ⎥ ⎢ mol ⎦ ⎣ ⎡ m3 ⎤ bace = 3.1.42748 R 2Tc2.427 We can also calculate a and b parameters for pure species using the following equations 0.081×10 − 5 ⎢ ⎥ ⎥ ⎢ mol ⎦ ⎣ Now. y ace = 0. convert the given quantities of acetylene and n-butane into moles.03 ⋅ 29.092) = 13.5 a= Pc b= 0. 2 2 amix = y1 a1 + 2 y1 y 2 a12 + y 2 a2 ⎡ J ⋅ K1/2 ⋅ m3 ⎤ a12 = 8. nace = 30 [kg ] 26.573 ybut = 0.038 × 10 -3 nbut = 50 [kg ] 58.

bmix = y1b1 + y 2b2 = 5.00111 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ ⎛ ⎡ m3 ⎤ ⎞ ⎜ ∴V = (nace + nbut )v = (1152. ⎡ m3 ⎤ v = 0.2 [mol] + 860.2 [mol]) 0.23 m 3 [ ] 64 .00111 ⎢ ⎥⎟ ⎜ mol ⎢ ⎥⎟ ⎣ ⎦ ⎝ ⎠ V = 2.53 × 10 −5 ⎡ m3 ⎤ ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ Substitution of the mixture parameters into the Redlich-Kwong EOS results in an equation with one unknown.

1. From Table A.4. ⎡ J ⋅ m 3 ⋅ K1/2 ⎤ a mix = 31.1 and A.17 ⎢ ⎥ Pc mol ⎥ ⎢ ⎦ ⎣ b1 = 0. we need to calculate the a and b parameters for species (1) and (2).40 × 10 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ ⎡ m 3 ⎤ ⎞ ⎛ 3 mol ⎞⎛ −4 ⎢ ⎥⎟ + ⎜ ⎟⎜1.1.7 [K ] Pc = 41.0 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ 65 .5 = 6.2 [K ] Pc = 73. bmix = y1b1 + y 2b2 ⎛ 2 mol ⎞⎛ −5 bmix = ⎜ ⎟⎜ 2.42748R 2Tc2.08664 RTc = 2.37 First.97 × 10 − 5 Pc ⎡ m3 ⎤ ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ a1 = b1 = Toluene (2): Tc = 591.01 m 3 V = = 0.036 × 10 − 4 Pc ⎡ m3 ⎤ ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ We can use the mixing rules to calculate bmix.76 [bar ] ⎡ J ⋅ m 3 ⋅ K1/2 ⎤ 0.002 ⎢ ⎥ 5 [mol] mol ntot ⎢ ⎥ ⎣ ⎦ [ ] We can then solve for amix. Note that the molar volume can be calculated as follows v= ⎡ m3 ⎤ 0.036 × 10 ⎟ ⎜ mol 5 mol ⎠⎝ ⎢ ⎥⎠ ⎝ ⎣ ⎦ ⎡ m3 ⎤ ⎞ ⎢ ⎥⎟ mol ⎢ ⎥⎟ ⎣ ⎦ ⎠ Now we can substitute the known values into the Redlich-Kwong EOS.5 a2 = = 61.466 ⎢ ⎥ Pc mol ⎢ ⎥ ⎣ ⎦ 0.08664 RTc = 1.42748R 2Tc2.97 × 10 ⎜ 5 mol ⎝ ⎠⎝ ⎡ 3⎤ −5 m bmix = 7.14 [bar ] ⎡ J ⋅ m 3 ⋅ K1/2 ⎤ 0.2: CO2 (1): Tc = 304.

79 states a12 = a1a 2 (1 − k12 ) Substitution of the values provides: k12 = 0. ⎡ J ⋅ m 3 ⋅ K1/2 ⎤ a12 = 16. we know ⎡ J ⋅ m3 ⋅ K1/2 ⎤ 2 2 amix = 31.From the mixing rules.0 ⎢ ⎥ = y1 a1 + 2 y1 y2 a12 + y2 a2 mol ⎢ ⎥ ⎣ ⎦ Therefore.55 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ Equation 4.17 66 .

561 ⎡ m3 ⎤ b⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ 6. ⎡ J ⋅ m3 ⎤ a⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ 0.564 0.38 × 10 −5 2. Because sizeC 2 H 6 > size H 2 O > size H 2 .4 y3 = 0.4.5 n1 + n2 + n3 10 mol y 2 = 0 . a23 . ⎡ J ⋅ m3 ⎤ a12 = a1a2 = 0.118 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ 3 ⎡J ⋅m ⎤ a13 = 0. bC 2 H 6 > bH 2 O > bH 2 .05 ×10 −5 Species C2H6 (3) H2 (1) H2O (2) These values are also consistent with what we would expect for the magnitude of van der Waals interactions given by a. a13 .025 0.78 to calculate a12 .119 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ 67 .81 and 4. Therefore. (b) The van der Waals parameters for the mixture can be calculated according to the mixing rules.1 y1 = Since binary interaction parameters are not available.38 (a) We can match the species by looking at the b parameter alone.82 2 2 2 a mix = y1 a1 + y1 y 2 a12 + y1 y3 a13 + y 2 y1 a21 + y 2 a 2 + y 2 y3 a 23 + y3 y1 a31 + y3 y 2 a32 + y3 a3 2 2 2 a mix = y1 a1 + 2 y1 y 2 a12 + 2 y1 y3 a13 + y 2 a2 + 2 y 2 y3 a 23 + y3 a3 bmix = y1b1 + y 2b2 + y3b3 Calculate mole fractions: n1 5 mol = = 0. From Equations 4. The b parameter is directly related to the size of the molecule.66 × 10 −5 3. we must use Equation 4.

00125 ⎢ ⎥ 10 mol mol n1 + n2 + n3 ⎢ ⎥ ⎣ ⎦ [ ] Therefore.562 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ Now we can find the numerical values for the van der Waals parameters. ⎡ J ⋅ m3 ⎤ amix = 0.19 × 10 − 5 ⎢ m ⎥ ⎟ ⎛ ⎜ 0.0125 m 3 V = = 0.92 MPa 68 . 206 ⎥ ⎢ ⎜ ⎟(300 K ) ⎜ 8.314 ⎢ mol ⋅ K ⎥ ⎟ mol ⎥ ⎢ ⎣ ⎦ ⎦ ⎣ ⎠ ⎝ P= − 2 3 3 ⎛ ⎤⎞ ⎡ ⎤ ⎡ ⎡ 3 ⎤⎞ ⎜ 0. the van der Waals equation is P= a RT − mix v − bmix v2 The molar volume is calculated as follows v= ⎡ m3 ⎤ 0.206 ⎢ ⎥ ⎢ ⎦ ⎣ mol ⎥ ⎡ m3 ⎤ bmix = 3.⎡ J ⋅ m3 ⎤ a23 = 0.19 × 10−5 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ (c) For the mixture.00125 ⎢ m ⎥ ⎟ ⎜ ⎥⎟ ⎢ mol ⎦ ⎥ ⎢ mol ⎦ ⎣ ⎣ ⎠ ⎜ ⎝ ⎢ mol ⎦ ⎥⎟ ⎣ ⎠ ⎝ P = 1. ⎡ J ⋅ m3 ⎤ ⎛ ⎡ J ⎤⎞ 0 .00125 ⎢ m ⎥ − 3.

b can be calculated as follows bmix = y1b1 + y 2b2 Using the Redlich-Kwong EOS.3 ⎢ ⎥ mol ⎢ ⎥ ⎣ ⎦ Therefore. But first. 2 2 Bmix = y1 B1 + 2 y1 y 2 B12 + y 2 B2 ⎛ ⎛ ⎛ ⎡ cm 3 ⎤ ⎞ ⎡ cm 3 ⎤ ⎞ ⎡ cm 3 ⎤ ⎞ 2⎜ ⎟ ⎜ ⎟ ( )( ) ( ) 0 . ⎡ J ⋅ K1/2 ⋅ m 3 ⎤ amix = 8. v= RT ⎛ Bmix ⎞ RT P⎟ = + Bmix ⎜1 + P ⎝ RT ⎠ P ⎡ cm 3 ⎤ ⎡ m3 ⎤ v = 2445.39 (a) To calculate the molar volume of the mixture.002446 ⎢ ⎥ mol mol ⎢ ⎥ ⎢ ⎥ ⎣ ⎦ ⎣ ⎦ (b) We can estimate k12 using an EOS where the a parameter is the only unknown.6 ⎢ ⎥ = 0.75⎜ 2. we will use the virial expansion in pressure since it is more accurate at moderate pressures.83 ×10 − 5 ⎜ ⎝ ⎛ ⎡ m3 ⎤ ⎞ −5 ⎢ ⎥ ⎟ + 0. ⎛ bmix = 0. 75 153 Bmix = (0.25⎜ 5. 75 110 2 0 .693 ⎢ ⎥ 2 mol ⎢ ⎥ ⎣ ⎦ Now we can calculate k12 as follows 2 2 a mix = y1 a1 + 2 y1 y 2 a12 + y 2 a2 69 .69 × 10 ⎢ ⎥ mol ⎦ ⎢ mol ⎦ ⎥⎟ ⎢ ⎥ ⎣ ⎣ ⎠ Substitute the known properties into the Redlich-Kwong EOS and solve for a.25)2 ⎜ − 625 ⎢ + − + − ⎥ ⎢ ⎥ ⎢ ⎥⎟ ⎜ ⎟ ⎜ ⎟ ⎜ ⎢ mol ⎦ ⎥⎠ ⎢ mol ⎦ ⎥⎠ ⎢ mol ⎦ ⎥⎟ ⎣ ⎣ ⎣ ⎝ ⎝ ⎝ ⎠ ⎡ cm 3 ⎤ Bmix = −158.97 ×10 ⎟ ⎜ mol ⎢ ⎥⎠ ⎣ ⎦ ⎝ ⎡ m3 ⎤ ⎞ ⎡ 3⎤ −5 m ⎢ ⎥ ⎟ = 3. we must calculate the second virial coefficient for the mixture.4. 25 0 .

35 6.79 a12 = a1a 2 (1 − k12 ) 8.81 k12 = 1 − = 0.03 70 .466 ⎢ ⎥ 2 ⎢ ⎥ ⎣ mol ⎦ ⎡ J ⋅ K1/2 ⋅ m 3 ⎤ ∴ a12 = 8.466 ⋅ 28.⎡ J ⋅ K1/2 ⋅ m 3 ⎤ a1 = 28.81 ⎢ ⎥ 2 mol ⎢ ⎥ ⎣ ⎦ (Calculated using Equation 4.03 ⎢ ⎥ 2 ⎢ mol ⎥ ⎣ ⎦ ⎡ J ⋅ K1/2 ⋅ m 3 ⎤ a2 = 6.47) From Equation 4.

they slow down even more than in the ideal gas case. Thus. If we had an equation of state that appropriately described the non-ideal behavior. During this isentropic process. we could apply the concepts of the thermodynamic web that we have learned in this chapter to solve for the final temperature.4. the only place that this can come from is the kinetic energy of the molecules.28 bar. additional energy must be supplied to “pull” the molecules apart. they will manifest themselves more in state 1 at the higher pressure than in state 2. the gas cools. (While T has some effect to counter this trend. Since the tank is insulated. Thus.40 During this process the gas in Tank A undergoes an expansion from 7 bar to 3. we expect it will be secondary to the effect of pressure). and the final temperature is lower. 71 . If attractive forces are present. in the nonideal case.

4.7% larger than the answer from ThermoSolver. 72 .41 Select the “Equation of State Solver” from the main menu. but the answer from the compressibility charts is only 5. The answer found using the Redlich-Kwong EOS is 16. we need to know the number of moles present in 10 kg.05812 [kg/mol] [ ] The answers provided in Example 4.07 × 10 − 4 ⎢ ⎥ ⎢ ⎣ mol ⎥ ⎦ To calculate the volume occupied by 10 kilograms of butane.1 [mol] 0.56% larger.1 [mol])⎜1.9 agree well with this answer. Enter the pressure and temperature and solve for the molar volume using the Lee-Kesler EOS. The program provides ⎡ m3 ⎤ v = 1. ⎛ V = (172. n= Therefore.018 m ⎟ ⎢ mol ⎦ ⎥⎠ ⎣ 10 [kg ] = 172.07 × 10 − 4 ⎜ ⎝ ⎡ m3 ⎤ ⎞ 3 ⎢ ⎥ ⎟ = 0.

only the answers are provided. 298 = −84.5711 % Difference 2. (a) Tc = 305.68 × 10 − 4 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ 0. thus.5859 Peng Robinson EOS ⎡ m3 ⎤ 3. Quantity v z (i).42 [K ] (c) The percent difference is calculated as follows ⎡ v LK − v PR ⎤ z LK − z PR % Difference = ⎢ or × 100⎥ % v LK z LK ⎣ ⎦ (i).4. Quantity v z Lee Kessler EOS ⎡ m3 ⎤ 3.7 2.1444 % Difference 4.42 Using ThermoSolver should be straightforward.68 ⎢ ⎥ ⎣ mol ⎦ (b) Tsat = 299.4 [K ] Pc = 48.84 [bar ] ⎡ kJ ⎤ ∆h o f .58 × 10 − 4 ⎢ ⎥ ⎢ mol ⎦ ⎥ ⎣ 0.1383 Peng Robinson EOS ⎡ m3 ⎤ 8.4 73 .34 × 10 − 5 ⎢ ⎥ ⎢ ⎣ mol ⎥ ⎦ 0.5 Lee Kessler EOS ⎡ m3 ⎤ 8.3 4.70 × 10 − 5 ⎢ ⎥ ⎢ ⎣ mol ⎥ ⎦ 0.

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tdq felix eel usp capitulo 4 aulas

tdq felix eel usp capitulo 4 aulas

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