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CHAPTER 4 THE PROPERTIES OF GASES

4.1

(a) 8 × 109 Pa;

(b) 80 kilobars;

(c) 6 × 107 Torr;

(d) 1 × 106 lb ⋅ in −2

4.3

(a) The difference in column height will be equal to the difference in pressure between atmospheric pressure and pressure in the gas bulb. If the pressures were equal, the height of the mercury column on the air side and on the apparatus side would be the same. The pressure in the gas bulb is
0.890 atm or 0.890 × 760 Torr ⋅ atm −1 = 676 Torr. The difference would

be 762 Torr – 676 Torr = 86 Torr = 86 mm Hg. of the atmosphere.

(b) The side attached to

the bulb will be higher because the neon pressure is less than the pressure (c) If the student had recorded the level in the atmosphere arm to be higher than the level in the bulb arm by 86 mm Hg then the pressure in the bulb would have been reported as 762 Torr + 86 Torr = 848 Torr. 4.5 d1 h1 = d 2 h 2 73.5 cm × 13.6 g ⋅ cm −3 = 909 cm or 9.09 m 1.10 g ⋅ cm −3

4.7

(20. in)(10. in)(14.7 lb ⋅ in 2 ) = 2.9 × 103 lb

SM-97

4.9

(a) Volume, L 0.01 0.02 0.03 0.04 0.05

nR , atm ⋅ K −1 V

8.21 4.10 2.74 2.05 1.64
nR V

(b) The slope is equal to

(c) The intercept is equal to 0.00 for all the plots. 4.11 (a) from PV 1 1 = P 2V2 , we have
(2.0 × 105 kPa) (7.50 mL) = (P2 ) (1000 mL); solving for P2 we get

1.5 × 103 kPa;

(b) similar to (a),

3 3 3 PV 1 1 = P 2V2 or (643 Torr) (54.2 cm ) = ( P 2 )(7.8 cm ), P 2 = 4.5 × 10 Torr

4.13

Using

P P P2 1.10 atm 1 ; P2 = 3.31 atm = 2 and expressing T in Kelvins, = 298 K 898 K T1 T2
4.15 Using

P P P2 1.5 atm 1 ; P2 = 1.6 atm = 2 and expressing T in Kelvins, = 283 K 303 K T1 T2 V1 V2 V1 V2 = . = , or 0.100 mol 0.110 mol n1 n2 n2V1 0.110V1 = = 1.10V1 . 0.10 n1

4.17

If P and T are constant, then

Solving for V2 in terms of V1 , we obtain V2 =

So the volume must be increased by 10.% to keep P and T constant.

SM-98

082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 ) (303 K) −1 ⎟ ⎝ 64.19 (a) Because P. V2 = 11.0 mL) ⎜ −1 ⎟ (0.4.255 atm)(35.5 mL) (1.314 51 L ⋅ kPa ⋅ K −1 ⋅ mol−1 )(287 K) SM-99 .06 g ⋅ mol ⎠ m = 0.91 g ⋅ mol−1 .0 Torr ⎞ V ⎜ −1 ⎟ ⎝ 760 Torr ⋅ atm ⎠ ⎛ 23.91 g ⋅ mol ⎠ V = 4.00 × 103 m3 ) ⎜ ⎟⎜ 3 ⎟ m3 (d) ⎝ ⎠ ⎝ 1000 cm ⎠ = n (8. ⎛ (500 Torr) ⎞ (12.969 atm 228 K 293 K (c) Similarly.9 × 10−3 g ⎞ =⎜ (0.0 mL) = ⋅ P2 = 0.1000 L) (c) ⎛ ⎞ ␮ =⎜ (0. T2 = 199 K 228 K T2 4.21 (a) Using the ideal gas law with the gas constant R expressed in kPa: P(0.06 × 102 mL (0.255 atm)(35. T1 T2 (0.1500 mol) (8.5 mL) ⎝ 760 Torr ⋅ atm ⎠ = .20 g ⎛ 1 × 106 cm3 ⎞ ⎛ 1 L ⎞ (129 kPa)(6. we can use the same expression.77 atm)(0.255 atm) (35.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 ) (373 K) −1 ⎟ ⎝ 136.8 mL = 228 K 298 K (b) The same relation holds as in (a) but here the final temperature and volume are known: (0. and T all change.00 atm)(V2 ) .06 × 103 kPa (b) BrF3 has a molar mass of 136. V.3500 L) = (0. P = 1.314 51 L ⋅ kPa ⋅ K −1 ⋅ mol−1 ) (297 K).5 mL) ( P2 )(12. with P and V known and T wanted. We then substitute into the ideal gas equation: ⎛ 10. we use the relation Substituting for the appropriate values we get PV PV 1 1 = 2 2.

32 L P 1 atm 4. We can simply use the ideal gas law in the form PV PV 1 1 = 2 2 T1 T2 ⎛ ⎞ 759 Torr (1.00 L) ⎜ −1 ⎟ ⎝ 760 Torr ⋅ atm ⎠ = 253 K ⎛ ⎞ 252 Torr (V2 ) ⎜ −1 ⎟ ⎝ 760 Torr ⋅ atm ⎠ 1523 K V2 = 18.0 × 10−6 L) = (6. V .00 kPa) (1.1 L 4.4 L P 1 atm (b) V = nRT (1 mol)(0. we can use SM-100 .24 × 105 mol CH 4 (e) The number of He atoms is the Avogadro constant N A multiplied by the number of moles.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(773 K) (a) V = = = 63.n = 3. and T are state functions.314 51 L ⋅ kPa ⋅ K ⋅ mol ) (158 K) ⎠ = 9.2 × 1014 atoms 23 −1 4.23 nRT (1 mol)(0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(77 K) = = 6. The number of moles is obtained from the ideal gas equation: PV = nRT PV N n= .27 Because T is constant. the intermediate conditions are irrelevant to the final states.022 × 10 atoms ⋅ mol ) ⎜ ⎟ −1 −1 ⎝ (8.25 Because P.n= RT NA so the number of atoms N will be given by ⎛ PV ⎞ N = NA ⎜ ⎟ ⎝ RT ⎠ ⎛ ⎞ (2.

082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(292.3 K 221.80 g ⋅ mol ⎠ PKr = ⎝ 0.18 atm 4.33 The pressure of the Ar sample will be given by ⎛ 2. Because volume.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(T2 ) ⎜ −1 ⎟ 83.00 × 10−3 g ⎞ (0.3 K 268.29 PV = nRT ⎛ ⎞ 24. they will cancel.7 K) n = 2.2 K V2 = 3. and the gas constant R are the same on both sides of the equation.2500 L) ⎜ −1 ⎟ ⎝ 101.239 L) P2 = 4. we can set these two equal to each other.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(293 K) ⎜ −1 ⎟ nRT ⎝ 39. SM-101 .6 m3 (b) PV PV 1 1 = 2 2 T1 T2 (104 kPa)(2.8 × 102 m3 4.00 L) = P2 (0.00 atm) (1.880 kPa) V2 = 294.31 (a) PV PV 1 1 = 2 2 T1 T2 (104 kPa)(2.PV 1 1 = P 2V2 (1.95 g ⋅ mol ⎠ PAr = = V 0.5 kPa (0.0 m3 ) (52 kPa) V2 = 294.050 0 L ⎛ 2.2 K V2 = 1.00 × 10−3 g ⎞ (0.325 kPa ⋅ atm ⎠ = n(0.050 0 L Because we want the pressure to be the same.0 m3 ) (0.52 × 10−3 mol 4. mass of the gases.

SM-102 . ⎛ ⎞ 200. 4.9.90 g ⋅ L−1 −1 −1 (0.81 atm = 70.28 g ⋅ L−1 d= (0. It might also be C2 H 4 F2 . for which M = 70 g ⋅ mol−1 . The order of increasing density will be CO < H 2S < CO 2 .082 06 L ⋅ atm ⋅ K ⋅ mol ) (373 K) 4. 44. g ⋅ mol−1 (b) The compound is most likely CHF3 . Torr (119.39 (a) M = dRT (8.01 g ⋅ mol−1 for H 2 S(g). See Section 4.37 (a) Density is proportional to the molar mass of the gas as seen from the ideal gas law. for which M = 66 g ⋅ mol−1 .01 g ⋅ mol−1 for CO(g). which in this case is CO2 . The most dense will be the one with the highest molar mass. 4.37 g⋅ mol−1 )(1.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(300.082 06 L ⋅ atm ⋅ K −1 ⋅ mol −1 )(298 K) (b) d = (119.⎛ ⎞ ⎛ ⎞ 1 1 (T ) = ⎜ (293 K) ⎜ −1 ⎟ 2 −1 ⎟ ⎝ 83. we obtain temperature = 615 K or 342°C. and 34.35 Density is proportional to the molar mass of the gas as seen from the ideal gas law: PV = nRT m PV = RT M density = mass per unit volume = m MP = V RT The molar masses of the gases in question are 28.0 g ⋅ L−1 )(0.01 g ⋅ mol−1 for CO 2 (g).37 g ⋅ mol−1 )⎜ −1 ⎟ ⎝ 760 Torr ⋅ atm ⎠ = 1.95 g ⋅ mol ⎠ Solving for T2 .80 g ⋅ mol ⎠ ⎝ 39. K) = P 2.00 atm) = 3.

The formula is C2 H 2 Cl2 . The problem may be solved using the ideal gas law: PV = nRT m PV = RT M mRT M = PV (3. 4.9 g ⋅ L ⎝ 2.47 g ⋅ mol−1 .00 atm ⎞⎛ 300.0 g .47g ⋅ mol−1 = 1.43 Density is proportional to the molar mass of the gas as seen from the ideal gas law: PV = nRT m PV = RT M density = mass per unit volume = m MP = V RT ⎛ ⎞ 53.755 L) n in the formula (CHCl) n is equal to 95.(c) You can use the relationship in (a) to calculate the new density.325 kPa ⋅ atm ⎠ 0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(273 K) M = = 95.98.9g ⋅ mol−1 ÷ 48.943 g ⋅ L−1 = (0. or you can apply the proportionality changes expected from the change in pressure and temperature to the original density: ⎛ 1. K ⎞ −1 d 2 = (8. an empirical formula of CHCl is calculated.557 g)(0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) M = 44.81 atm ⎠⎝ 298 K ⎠ 4. The empirical formula mass is 48. mol−1 SM-103 .41 From the analytical data.0 g ⋅ L−1 )⎜ ⎟⎜ ⎟ = 2.10 atm)(0.9 g ⋅ mol−1 (1.1 kPa M⎜ −1 ⎟ ⎝ 101.

0 × 105 L) (376 atm)V2 = 623 K (523 K) V2 = 1.00 atm ( ) = 3. as are the temperature and pressure.0 × 105 L (b) The ideal gas equation PV PV PV PV 1 1 = 2 2 simplifies to 1 1 = 2 2 n1 RT1 n2 RT2 T1 T2 because R and n are constant for this problem.5 times the amount of NH3 produced. ⎛ ⎛ 3 mol H 2 ⎞ (1.0 × 104 L We need to find the number of moles of CH 4 (g) present in each case.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(623 K) ⎜ ⎟⎜ −1 ⎟ 2 ⋅ 17.4.03 g mol ⎝ ⎠⎝ ⎠ = 15. We will use the ideal gas equation to solve for n in the first case: 4. the larger number of moles of CH 4 (g) should produce the larger volume of CO 2 (g). Because the combustion reaction is the same in both cases.03 g mol nH2 RT ⋅ 2 nNH3 RT 3 ⎠ ⎝ ⎠ V = = =⎝ P P P 6 ⎞ 10 g ⎛ 3⎞ ⎛ (0.00 atm)(3.0 × 103 kg)(103 g ⋅ kg −1 ) ⎞ ⎜ ⎟ 3 −1 ⎜ ⎜ 2 mol NH ⎟ ⎟ RT 17. as seen from the balanced equation: 1 2 N 2 (g) + 3 2 H 2 (g) → NH 3 (g) or N 2 (g) + 3 H 2 (g) → 2 NH 3 (g) Once the number of moles is known. the volume can be obtained from the ideal gas law. (15.45 (a) The number of moles of H 2 needed will be 1.47 SM-104 .

determine the number of moles of CO 2 needed.49 4.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(303 K) ⎛ ⎞ 150 Torr (0. From this.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(348 K) 2.124 mol 2.00 g = 0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) = 2. The molar mass of glucose is 180.15 g glucose ⋅ mol glucose ⎠ ⎝ 1 mol glucose ⎠ ⎦ ⎣ V = ⎛ 0.00 atm)(2.15 g ⋅ mol−1 .082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) nNH3 nHCl SM-105 .00 g of CH 4 will be 16.26 Torr ⎞ ⎜ −1 ⎟ ⎝ 760 Torr ⋅ atm ⎠ × (0.94 × 10−5 mol RT (0. With that information and the other information provided in the problem. we can calculate the number of moles of glucose formed and. Our first task is to determine the number of moles of NH3 and HCl that are present to start with.51 (a) This is a limiting reactant problem.(1.00 L) PV = = 0. using the reaction stoichiometry.4 × 104 L 4.02 × 10−4 mol RT (0.0150 L) ⎜ −1 ⎟ 760 Torr atm ⋅ PV ⎝ ⎠ = = = 7.0 g glucose ⎢⎜ ⎟⎜ ⎟⎥ −1 ⎝ 180.04 g ⋅ mol−1 n= The latter case will have the greater number of moles of CH 4 and should produce the larger amount of CO 2 (g).0250 L) ⎜ −1 ⎟ 760 Torr ⋅ atm PV ⎝ ⎠ = = = 2. we can use the ideal gas law to calculate the volume of air that is needed: PV = nRT ⎡⎛ ⎞ ⎛ 6 mol CO2 ⎞ ⎤ 10. This can be done from the ideal gas equation: PV = nRT ⎛ ⎞ 100 Torr (0.0700 mol CH 4 RT (0.

0 mol of ideal gas will exert a pressure of 1.0161 mol. we can calculate the mass of NH 4 Cl that forms: (7.23 × 10−4 mol HCl left after the reaction. the partial pressure of H2 (g) will be 2.0757 atm 0.0 atm. we use the ideal gas law to determine the final pressure: PV = nRT P= (1.25 × 10−3 g (b) There will be (2.0 atm + 2.150 L) PV = = 0.0223 − 0. pressure will be 1.0400 L 4. PV = nRT ntotal = nN2 = (1.0400 L.006 17 mol RT (0.53 (a) The molar volume of an ideal gas is 22. The initial data gives us the total number of moles present. (b) The total 4.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(300 K) = 0.15 K.0 atm under those conditions. Because there are 2. From the molar mass of NH 4 Cl (53.0 atm. The partial pressure will be given by the mole fraction multiplied by the SM-106 .The ammonia is the limiting reactant. The number of moles of NH 4 Cl(s) that form will be equal to the number of moles of NH3 that react.94 × 10−5 mol) = 1.49 g ⋅ mol−1 ) = 4. whereas the data for the gas sample after being passed over CaSO3 (s) represents the number of moles of N 2 (g).0 mL or 0.0223 mol RT (0.49 g ⋅ mol−1 ) and the number of moles.09 atm)(0.94 × 10−5 mol NH 4 Cl(s))(53.4 L at 273. This quantity will exist in a total volume after mixing of 40. Again.02 × 10−4 mol − 7.09 atm)(0.500 L) PV = = 0.0 atm = 3.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(323 K) The number of moles of SO 2 gas is 0.0 atm. The partial pressure of N 2 (g) will be 1.006 17 mol = 0. 1.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) (1.0 mol of H 2 (g) .55 (a) We find the pressure of SO 2 (g) originally present by difference.23 × 10−4 mol)(0.

004 45 mol. The pressure due to H 2 (g) will.2 Torr ⎞ (0.54 Torr = 739.722)(1. therefore.54 Torr will be due to water vapor. (c) To answer this question.722. The mole fraction of SO 2 (g) will be 0.004 45 mol)(32.59 Graham’s law of effusion states that the rate of effusion of a gas is inversely proportional to the square root of its molar mass: rate of effusion = 1 M Diffusion also follows this relationship. so the number of moles of O 2 = 0. The mass of O2 will be given by (0. we can take the ratio SM-107 .57 (a) Of the 756.0161 mol)(64.787 atm. 4. (b) H 2 O(l) → H 2 (g) + 1 2 O 2 (g).142 g. be 756. we can set up the following: ⎛ 739.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(293 K) ⎜ −1 ⎟ 760 Torr atm ⋅ ⎝ ⎠ Solving for n. According to the stoichiometry of the reaction.06 g ⋅ mol−1 ) = 1.03 g 4. we must determine the number of moles of H 2 produced in the reaction.00 g ⋅ mol−1 ) = 0. Using the partial pressure of H 2 calculated in part (a) and the ideal gas equation.008 90 mol.0223 mol = 0. half as much oxygen as hydrogen should be produced.7 Torr − 17.09 atm) = 0. we obtain n = 0.0161 mol ÷ 0.total pressure. The pressure due to SO 2 in the original mixture is (0. 17.7 Torr measured. (b) The mass of SO 2 will be obtained by multiplying the number of moles of SO 2 by the molar mass of SO 2 : mSO2 = (0.220 L) = n(0.2 Torr. If we have two different gases whose rates of diffusion are measured under identical conditions.

95 g ⋅ mol 1 N M1 147 s 147 s M2 M1 In order to calculate the time of effusion.24 = 1 83. we need to know only the molar mass of the gases. SM-108 . N will be the same for argon and for the second gas chosen. the rate of diffusion of Kr is 1.1 rate1 = rate2 M1 = 1 M2 If a compound takes 1.24 times as long to diffuse as Kr gas.61 The rate of effusion is inversely proportional to the square root of the molar mass. We can now use the expression to calculate the molar mass of the unknown. Using a ratio as follows allows us to calculate the time of effusion without knowing the exact conditions of pressure and temperature: 1 rate1 = rate2 M1 = 1 M2 The rate will be equal to the number of molecules N that effuse in a given time interval. For the conditions given. given the mass of Kr: M2 1.80 g ⋅ mol−1 M 2 = 129 g ⋅ mol −1 M2 M1 A mass of 129 g ⋅ mol−1 corresponds to a molecular formula of C10 H10 . N 1 −1 time = time = 39.24 times that of the unknown. 4.

06 g ⋅ mol−1 147 s time = 186 s 4.95 g ⋅ mol−1 28.63 The formula mass of C 2 H 3 is 27.0 s (d) For SO 2 with a molar mass of 1 timeCO2 39.95 g ⋅ mol−1 −1 2.01 g ⋅ mol : = 1 2.(a) For CO 2 with a molar mass of 1 timeCO2 39.04 g ⋅ mol−1 .01 g ⋅ mol−1 147 s time = 154 s (b) For C 2 H 4 with a molar mass of 1 timeC2H4 39.01 g ⋅ mol−1 147 s time = 33.01 g ⋅ mol−1 : = 1 44.95 g ⋅ mol−1 44. we can write alternatively SM-109 .95 g ⋅ mol−1 64.05 g ⋅ mol−1 147 s time = 123 s (c) For H 2 with a molar mass of 1 timeCO2 39.05 g ⋅ mol−1 : = 1 28. we can calculate the molar mass of the sample.06 g ⋅ mol−1 : = 1 64. 1 rate1 = rate2 M1 = 1 M2 M2 M1 Because time is inversely proportional to rate. From the effusion data.

4.09 g ⋅ mol−1 −2 SM-110 .95 g ⋅ mol−1 210 = M1 349 M 1 = 110 g ⋅ mol−1 The molar mass is 4.65 (a) The average kinetic energy is obtained from the expression: average kinetic energy = 3 2 RT .314 kg ⋅ m 2 ⋅ s −2 ⋅ K −1 ⋅ mol−1 )(253 K) 1. The numerical values are: (a) 4103.67 The root mean square speed is calculated from the following equation: c= 3 RT M (a) methane.5 J ⋅ mol−1 4. (c) 4103.007 × 10−2 kg ⋅ mol−1 = 458 m ⋅ s −1 (c) propane.314 kg ⋅ m 2 ⋅ s ⋅ K −1 ⋅ mol−1 )(253 K) c= 3.2 J ⋅ mol−1 − 4090.07 g ⋅ mol −1 3(8.2 J ⋅ mol−1 .1 times that of the empirical formula mass. M = 16. The value is independent of the nature of the monatomic ideal gas. (b) 4090.604 × 10−2 kg ⋅ mol−1 = 627 m ⋅ s −1 (b) ethane.7 J ⋅ mol−1 . M = 44. C3 H 8 .7 J ⋅ mol−1 = 12.95 g ⋅ mol−1 = 1 M1 210 s 39.1 349 s 39. so the molecular formula is C8 H12 . CH 4 . C 2 H 6 . M = 30.04 g ⋅ mol −1 c= 3(8.

95 ⎠ ⎝ 467 ⎠ = 3.9977) ⎝ 39.00×10−3 kg/mol)(1477 m/s)2 − (39.314 J ⋅ K -1 ⋅ mol-1 ) = 349.9 K Use the Maxwell Distribution of Speeds (Equation 4.9 K) 2(8.00 ⎞ ⎛ 1477 ⎞ =⎜ ⎟ ⎜ ⎟ (0.69 Use the expression for the root mean square speed to determine the temperature.409 × 10−2 kg ⋅ mol−1 = 378 m ⋅ s −1 4. ν rms = 3RT M 2 ν ⋅ M (1477 m ⋅ s −1 )2 ⋅ (4.29) appropriately for both gases: − M He (ν He ) ⎛ M ⎞2 2 RT 4π N ⎜ He ⎟ (ν He ) 2 e f (ν He ) RT 2 ⎝ ⎠ = 1 f (ν Ar ) − M Ar (ν Ar )2 ⎛ M Ar ⎞ 2 2 2 RT 4π N ⎜ ⎟ (ν Ar ) e ⎝ 2 RT ⎠ 2 1 = ( M He ) 2 (ν He )2 e 1 − M He (ν He )2 − M Ar (ν Ar ) 2 2 RT ( M Ar ) (ν Ar )2 e 1 2 2 RT = ( 4.c= 3(8.314 kg ⋅ m 2 ⋅ s −2 ⋅ K −1 ⋅ mol−1 )(253 K) 4.95 g ⋅ mol ) -1 1 2 (467 m ⋅ s-1 ) 2 × 1 2 e e − (4.314 J/(K ⋅mol))(349.16 SM-111 .314 J/(K ⋅mol))(349.95×10−3 kg/mol)(467 m/s)2 1 2 2(8.00 g ⋅ mol-1 ) 2 (1477 m ⋅ s-1 )2 1 ( 39.9 K) ⎛ 4.00 × 10−3 kg ⋅ mol-1 ) = T = rms 3R 3(8.

but at high pressures there is a very significant differences.9.04267 L ⋅ mol−1 ) ⎝ ⎠ ⎛ (3. At low temperatures. (c) 489 atm. thus lowering the pressure. (c) 1. van der Waals equation: 48. we obtain P = (a) 1.640 L2 .00 mol)(0.00 mol)(0.88 × 103 atm. SM-112 . we calculate for P = (a) 1. the ideal gas law gives essentially the same values as the van der Waals equation. atm .002 ) ⎞ −⎜ ⎟ V2 ⎝ ⎠ Using the three values for V.00 mol)(0.9 atm. Note that at low pressures.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) ⎞ =⎜ ⎟ V − (1. this hydrogen bonding causes the molecules of HF to be attracted to each other more strongly. 4. As the temperature is increased. The calculations can now be repeated using the ⎛ an 2 ⎞ + P ⎜ ⎟(V − nb) = nRT V2 ⎠ ⎝ We can rearrange this to solve for P : ⎛ nRT ⎞ ⎛ an 2 ⎞ P=⎜ ⎟−⎜ 2 ⎟ ⎝ V − nb ⎠ ⎝ V ⎠ ⎛ (1.75 The pressures are calculated very simply from the ideal gas law: P= nRT (1.62. the hydrogen bonds are broken and the pressure rises more quickly than for an ideal gas.63 atm. 4.71 (a) The most probable speed is the one that corresponds to the maximum on the distribution curve. (b) 38. Dimers (2 HF molecules bonded to each other) and chains of HF molecules are known to form. mol−2 )(1. (b) The percentage of molecules having the most probable speed decreases as the temperature is raised (the distribution spreads out).4.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) = V V (b) Calculating for the volumes requested.73 Hydrogen bonding is important in HF.

042 67 L ⋅ mol−1 ) ⎝ ⎠ −1 2 2 ⎛ (3.300 7.67 P ideal − P van der Waals × 100 P van der Waals (b) Consider one point.82 7.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(300 K) ⎞ =⎜ ⎟ 1.77 The values for the pressures of gas with varying numbers of moles of CO 2 present are calculated as follows: The ideal gas law values are calculated from P= nRT V values for the van der Waals equation can be obtained by rearranging the equation: ⎛ an 2 ⎞ P + (V − nb) = nRT ⎜ 2 ⎟ V ⎝ ⎠ ⎛ nRT ⎞ ⎛ an 2 ⎞ P=⎜ ⎟−⎜ 2 ⎟ ⎝ V − nb ⎠ ⎝ V ⎠ ⎛ (n) (0.44 11.100 2.640 L ⋅ atm ⋅ mol ) (n ) ⎞ −⎜ ⎟ (1.5 0. The term V − nb will increase the ideal value nRT by 1.00 L) 2 ⎝ ⎠ The resulting values are n Pideal Pvan der Waals % deviation* 0.400 9.200 4.02 atm versus 9.38 0.58 atm. for example. the case for n = 0.2 4.44 4.4.3 5.00 L − (n)(0.500 12.85 0.9% over the ideal gas value.1 3. SM-113 .400 mol.31 *% deviation = 2.85 atm) whereas the correction from an 2 will V2 decrease the value by 0.8 2.15 9. a change of 5.7% of the ideal value V (10.46 0.92 0.

dominates in this case.79 Ammonia: a = 4.6 0. .05 0.. ammonia P. (c) The gas starts to deviate from ideality by more than 5% at pressures above about 10 atm. which is due to the intermolecular attractions.The second effect. b = 0.037 07 L ⋅ atm −1 Oxygen: a = 1. This may likely arise because ammonia is more polar and will have stronger intermolecular interactions. ..5 0. ideal 3581 811 256 140 94 70 55 46 39 34 30 1897 497 180 106 75 58 47 39 34 30 27 489 245 122 82 61 49 41 35 31 27 24 Clearly.3 0.7 0..225 L2 ⋅ atm ⋅ mol−2 .8 0.4 0. . O N O SM-114 .81 (a) O . .. oxygen P.1 0. ..9 1 P..2 0. Ammonia deviates more strongly and its van der Waals constants are larger than those for oxygen.378 L2 ⋅ atm ⋅ mol−2 .. b = 0. the greates deviation from the ideal gas law values occurs at low volumes or higher pressures. .. . .. . 4. N O . ..0318 83 L ⋅ atm −1 Volume 0. 4.

082 06 L ⋅ atm ⋅ K ⋅ mL )(293 K) (760 Torr) (1000 mL) = 7.020 ppm 5.064 × 1015 NO 2 molecules = 0.32 × 1022 molecules total 4. E photon = hc (6.83 Use the ideal gas law to calculate the number of moles of HCl.006 × 10 = 1.(b) Since the wavelength of the absorbed photons is 197 nm.07 mJ must be equal to the number of NO2 molecules.55 × 10−3 mol HCl Since the reaction between HCl and NaOH occurs in a 1:1 mole ratio.85 atm)(2. Torr)(200.07 mJ ⎜ ⎟⎜ -18 ⎝ 1000 mJ ⎠⎝ 1. this number of moles of NaOH is also present in the volume of NaOH(aq) required to reach the stoichiometric point of the titration.064 × 1015 ⎞ ⎟ J⎠ NO 2 molecules The pressure is created by all the molecules in the sample.5 L) × ⎜ ⎟ -1 -1 ⎝ (0.626 × 10−34 J ⋅ s)(2. n= PV (690. the proportion of NO2 molecules in the sample is 1.998 × 108 m ⋅ s −1 ) ⎛ 109 nm ⎞ ⎜ ⎟ 197 nm ⎝ m ⎠ λ = = 1. the molarity of the NaOH solution is SM-115 . mL) (1 atm) (1 L) = ⋅ ⋅ −1 −1 RT (0.006 × 10−18 J The number of photons in 1. ? molecules total=N AV × ntot = N AV × PtotV RT 23 = (6. Therefore.022 × 10 molecules ⋅ mol-1 ) ⎛ ⎞ (0.08206 L ⋅ atm ⋅ K ⋅ mol )(293 K ⎠ = 5. we can find the energy per photon.32 × 1022 molecules total Therefore. ⎛ 1 J ⎞⎛ 1 photon ? photons = 1.064 × 1015 photons=1. so the ideal gas law can be used to find the total molecules.

02 g ⋅ mol ⎠ =⎝ 5.01 g ⋅ mol ⎠ =⎝ 5.96 atm (2.55 × 10−3 mol NaOH) 1000 mL = ⋅ 1 L of solution (15.78 g (0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) ntotal = 0.85 (a) N 2 O 4 (g) → 2 NO 2 (g). so another relationship is needed.00 L) = ntotal (0.moles NaOH (7.00 L = 2. (b) If all the gas were N 2 O4 (g). The total pressure at the end of the reaction will give us the total number of moles present: Ptotal = 2.78 g (0.481 M 4.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) ⎜ −1 ⎟ 46.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) ⎜ −1 ⎟ 92.65 atm (d) Because both N 2 O 4 and NO 2 are present.605 mol ∴ nN 2 O4 + nNO2 = 0. we need to determine some way of calculating the relative amounts of each present.00 L = 4. We can take advantage of knowing the stoichiometry of the reaction. If we assume that all of the gas begins at N 2 O 4 and we allow some to react. then the moles can be calculated from the ideal gas equation: P= nRT V ⎛ ⎞ 43.7 mL) 1L = 0. This can be done by taking advantage of the gas law relationships.605 mol This gives us one equation.33 atm (c) The only difference in the calculation between part (b) and part (c) is that the molar mass of NO 2 is half that of N 2 O 4 .96 atm)(5. we can write the following: SM-116 . P= nRT V ⎛ ⎞ 43. but we have two unknowns.

81 atm)(0. The formula unit has a mass of 16.02 g ⋅ mol−1 .129 mol nNO2 = 2 x = 2(0.476 mol − x = 0.605 mol = 0.605 mol X NO2 X N 2 O4 4. there will be 0.200 L) The molar mass divided by the mass of the empirical formula mass will give the value of n in the formula SM-117 .258 mol nN2O4 = 0.129 mol) = 0.574 0. and temperature data will allow us to calculate the molar mass. pressure.347 mol 0.473 g)(0.87 (a) The elemental analyses yield an empirical formula of NH 2 .476 – x mole of N 2 O 4 and 2x mole NO 2 . The mass. volume.Initial amount of N 2 O 4 0.258 mol = = 0.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) M = = = 31.476 − x) + 2 x = ntotal 0.605 mol 0.476 mol Amount of N 2 O 4 that reacts x (mol) Amount of NO 2 formed 2x (mol) When the reaction is completed.426 0.9 g ⋅ mol−1 PV (1. using the ideal gas equation: PV = nRT PV = m RT M mRT (0.476 mol + x x = 0. The total number of moles will be given by: (0.347 mol = = 0.

0 min ⎛ 3.02 g ⋅ mol−1 = 1. which corresponds to the molecule known as hydrazine. 31.5 × 10−4 mol ⎞ 17.29 (the Maxwell Distribution of Speeds): − M (10ν rms ) ⎛ M ⎞2 2 RT 4π N ⎜ (10ν rms ) 2 e ⎟ f (10ν rms ) ⎝ 2 RT ⎠ = 1 f (ν rms ) − M (ν rms )2 ⎛ M ⎞2 2 2 RT 4π N ⎜ ⎟ (ν rms ) e ⎝ 2 RT ⎠ 2 1 4. SM-118 .05 g ⋅ mol−1 ⎝ 15. (b) H N H .0 min 32.9 g ⋅ mol−1 ÷ 16.03 g ⋅ mol−1 (25.0 min ⎠ = 4. N H H (c) rateA = rateB MB MA 3.03 g ⋅ mol−1 25.5 × 10−4 mol 15..99. It makes sense that the ratio should become bigger at higher temperatures as the distribution spreads out such that the number of molecules with higher speeds increases while the number with lower speeds decreases.0 min) X =⎜ ⎟ 32. .89 = 100ν 2 rms e 2 − M 100ν rms 2 RT 2 ν rms e 2 − Mν rms = 100e ( 2 − M 100ν rms 2 RT + 2 Mν rms 2 RT ) 2 RT = 100e 2 −99 Mν rms 2 RT The ratio is not independent of temperature since the variable T appears in the denominator of a negative exponent on e.(NH 2 )n .2 × 10−4 mol Using ν rms = root mean square speed and Equation 4.05 g ⋅ mol−1 = X 17. so the molecular formula is N 2 H 4 ..

phosgene By the stoichiometry. must be adjusted to the new temperature: ⎛ 500 K ⎞ Pinitial.75 atm x = 0.75 (b) The gas density will not change over the course of the reaction because the steel cylinder is a fixed size. CO = Pinitial.02 atm ⎝ 298 K ⎠ ⎛ 500 K ⎞ Pinitial.61 atm − 0.75 atm)⎜ ⎟ = 4. chlorine + Pfinal.88 = 0.4.75 5. Cl2 .02 atm − 0. The density can be calculated from the relationship SM-119 .91 The gases react according to the equation: CO(g) + Cl2 (g) → COCl2 (g) (a) We can write the following relationship based upon the stoichiometry of the reaction: Pfinal = Pfinal. we can write Pfinal. CO = 6. CO + Pfinal. CO − x + Pinitial.73 = = 0.88 atm = 3. chlorine = Pinitial.61 atm − x = 9. chlorine − x Pfinal = Pinitial.02 atm + 4.75 3. CO − x Pfinal. however. CO.73 atm The mole fractions are proportional to the pressure so we can write X COCl2 = X CO X Cl2 0. CO − x + x = Pinitial.59 atm)⎜ ⎟ = 6.383 9.88 atm = 5.090 9. 223°C = (3. 223°C = (2. phosgene = x Pfinal. CO − x The initial pressures.61 atm ⎝ 298 K ⎠ Pfinal = 6.88 atm Pfinal. chlorine = 4.14 = = 0. CO + Pinitial.527 9.14 atm Pfinal.

082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) (2. but we can calculate the density from the individual densities of the gases put into the cylinder initially.93 The two scents will diffuse according to Eqn 4. 4. Because no mass is added or subtracted from the cylinder and its volume does not change.d= m V PM = RT We do not know the mass of samples added.90 g ⋅ mol−1 ) (0.889 m .51 atm)(28. or x =0.01 g ⋅ mol−1 ) (0.889 172 Let x = the distance traveled by ethyl octanoate (fruity) and y = the distance traveled by p-anisaldehyde (minty) in the same amount of time.45 g ⋅ L−1 + 4.45 g ⋅ L−1 d Cl2 = = 4.889y = 1m y Substituting for x gives SM-120 . nor the volume of the container. Then x+ y =5m and x 0. the density will be the same at the end of the reaction as at the beginning. d COCl2 = = PM RT (3. ratefruity rateminty = M C8H8O2 M C10 H20O2 = 136 = 0.75 g ⋅ L−1 = 7.75 atm)(70.75 g ⋅ L−1 d total = 2.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(298 K) = 2.20 g ⋅ L−1 One could do a similar calculation for all three gases at 500 K to obtain the same answer.19.

the answers are 2 m and 3 m respectively.509 g)(0.65 m.235 L) ⎜ −1 ⎟ ⎝ 760 Torr ⋅ atm ⎠ = 254 g ⋅ mol−1 If the molecular formula is OsO x . the volume.35 m away from the north end of the room where the fruity smell originates in order to smell the minty scent first. 4.2 g ⋅ mol−1 + x(16. then the molar mass will be given by: 190. If we round off to 1 SF for each distance.99 The formula is OsO 4 .889 y + y = 5 1. we can resort to using the ideal gas equation rearranged to group the constant terms on one side of the equation: SM-121 .97 In this problem.0.95 The molar mass calculation follows from the ideal gas law: PV = nRT m PV = RT M mRT (1. and molar mass of the substance stay constant.00 g ⋅ mol−1 ) = 254 g ⋅ mol−1 ) x = 3. A person must stand more than 2. In order to calculate the new mass with the same conditions.35 m in the same time that the minty smell will travel 2.) 4.082 06 L ⋅ atm ⋅ K −1 ⋅ mol−1 )(473 K) = M = PV ⎛ ⎞ 745 Torr (0.889 y = 5 y = 2.65 So the fruity smell will travel 5-2. (Note: the problem only gives 1 SF for the length of the room.65=2. pressure.

1 g The mass of gas released must therefore be 46. K).2 g)(300. P. therefore m2 = 23.1 g.370 × 10−2 L ⋅ mol−1 ÷ 6. is 4 V = π r3 3 4 = π (128 pm)3 3 = 8.78 × 106 pm3 (c) The difference in these values illustrates that there is no easy definition for the boundaries of an atom.936 × 10−23 cm3 ⋅ atm −1 3. owing perhaps to longer range and weak interactions between atoms.2 g − 23.936 × 10−26 L ⋅ atom −1 3. The volume of the He atom.936 × 10−23 cm 3 ⋅ atm −1 × (1010 pm ⋅ cm −1 )3 = 3. (a) volume of one atom = molar volume ÷ Avogadro’s number 2. for which so we can set them equal: m1T1 = m2T2 (46.99 (b) The atomic radius of He is 128 pm (Appendix 2D).PV = nRT m PV = RT M but M .936 × 10−26 L ⋅ atom −1 × 1000 cm3 ⋅ L−1 = 3.936 × 107 pm3 4 3. One should also bear in mind that the value for the van der SM-122 . 1 and 2. so we can write MPV = mT R Now we have two sets of conditions. based upon this radius.1 g = 23. K) = ( m2 )(600. and V are constants.936 × 107 pm3 = π r 3 3 r = 211 pm MPV is constant R 4.022 × 1023 atoms ⋅ mol−1 = 3. The van der Waals value obtained from the correction for molar volume is considerably larger than the atomic radius.

.. P. SM-123 ..002 L)V 2 + (0.505 mol)3 (4. R.08206 L ⋅ atm ⋅ K -1 ⋅ mol-1 )(298 K) + (3. (d) trigonal planar 4. . then solve for V.225 L2 ⋅ atm ⋅ mol-2 )(3.505 mol) 3 ⎛ (0. N O . or − 0. . .0979 L (b) Compare the volume calculated in part (a) to that of an ideal gas under the same conditions. 4.505 mol) (4.. solve graphically for the three roots or use an appropriate program such as Math Cad.. .101 (a) ClNO2 (b) ClNO2 (c) O . N O ..09789 L but only the positive root is physically possible.1089.. and its interpretation is more complicated than a simple molar volume.0 atm) ⎞ 2 ×⎜ ⎟V (95.. . Cl .Waals b is a parameter used to obtain a good fit to a curve. .0 atm) ⎝ ⎠ − (0.103 (a) Substitute the van der Waals parameters for ammonia as well as the given values of n. Only one of the three roots is physically possible: 2 n3 ab ⎛ RT + bP ⎞ 2 ⎛ n a ⎞ V + n⎜ =0 ⎟V − ⎟V + ⎜ P P ⎝ ⎠ ⎝ P ⎠ V 3 + (0.991.707 L ⋅ mol-1 )(95. or 0.. so V = 0.... .01134 L2 )V − 0. . Since the equation is cubic.0 atm) V 3 + (2. O . .0 atm) ⎝ ⎠ 2 2 -2 ⎛ (0. Cl ...225 L ⋅ atm ⋅ mol ) ⎞ +⎜ ⎟V (95.. . and T into the vdW equation.02123 L3 = 0 V = −1.707 L ⋅ mol-1 ) =0 (95..

0 atm Videal = 0. reducing the effective number of moles of gas.130 L 95.130 L < VvdW. or “real”.08206 L ⋅ atm ⋅ K -1 ⋅ mol-1 )(298 K) = 0.0979 L. = 0. gas occupies less volume than the “ideal” gas. SM-124 . If the molecules are attracted to one another they will behave less independently.505 mol)(0.PV = nRT V = (0. Attractive forces dominate because the van der Waals.