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Homework 2 Answer

(Due 01/26/2011 Wednesday)

1. (a) Calculate the molar volume, temperature, pressure of N2 at the critical point using van
der Waals parameters a and b (see Table 1.1). (b) Obtain the density of N2 at the critical
point, and compare it with that of liquid N2 (~0.8 g/mL). Assume that the molar mass of
N2 is 28.0.
a)
at critical point
a 8a
VC  3b PC  TC 
27b 2 27Rb
VC  3b  3  0.0387 Lmol 1  0.1161Lmol 1

a 1.370L2 barmol-2
PC    33.88bar
27b 2
27  (0.0387 Lmol 1 ) 2

8a 8 1.370L2 barmol-2
TC    126.2 K
27Rb 27  0.0831447 LbarK 1mol 1  0.0387 Lmol 1
b)
Density at critical point:
28.0gmol-1
D  0.241g / mL
1000mL
0.1161Lmol-1 
1L
2. Assume Tc ~ 2Tm. Answer which of He, Ar, CO2, N2,
H2O have the highest and lowest Tm based on Tc
estimated from Table 1.1. Give reasoning with
calculations of Tm.
H2O has the highest Tm, He has the lowest Tm.
1 1 8a 4 a
Tm ~ Tc   
2 2 27 Rb 27 R b
Tc(K) Tm(K)
He 5.2 2.6
Ar 151 75
CO2 304 152
N2 126 64
H2O 647 323

3. Calculate the pressures for (a) He and (b) H2O from van der Waals equation when the
molar volume is 0.6 L and 310 K.
a)
RT a 0.08314dm3barK -1mol -1  310 K 0.0346 L2barmol -2
PHe   2    44.73bar  0.096bar  44.6bar
Vm  b Vm 0.6000 Lmol 1  0.0238Lmol 1 (0.6000 Lmol 1 ) 2

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b)
RT a 0.08314dm3barK -1mol -1  310 K 5.537 L2barmol -2
PH 2 O   2    45.25bar  15.38bar  29.87bar
Vm  b Vm 0.6000 Lmol 1  0.03049 Lmol 1 (0.6000 Lmol 1 ) 2
4. (From Atkins Ch1)
The critical constants of ethane are Tc = 309.15 K, Vmc = 112.7 cm3 mol-1. (a) Calculate the
van der Waals parameters of the gas. (b) Calculate the critical pressure pc. (c) Estimate
the radius of the molecules.

a)
a 8a
VC  3b PC  TC 
27b 2 27Rb

Van der Waals parameters:

VC 112.7cm3 mol-1
b   37.57cm3mol 1  0.03757 Lmol 1
3 3

27 RbTc 27  0.08206 L  atm  mol 1 K 1  0.03757 Lmol 1  309.15K


a   3.217atm  L2  mol 2
8 8

b)
a 3.217atmL2 mol 2
PC    84.41K
27   0.03757 Lmol 1 
2 2
27b

c)
Van der Waals volume:
b 37.57cm3 mol 1
VW    6.238 1023 cm3 / molecule
N A 6.022 1023 molecule / mol

4
VW   rW 3
3

Molecule radius:

3 3
rW  3 VW  3  6.238 1023 cm3 / molecule  2.5 108 cm  0.25 109 m  0.25nm
4 4

5. Can you use the van der Waals equation below critical temperature of the gas? If so what
kind of caution or modification is needed?

Yes, we can use van der Waals equation below critical temperature.

Above the critical temperature the van der Waals equation is an improvement of the ideal gas
law, and for lower temperatures the equation is also qualitatively reasonable for the liquid state
and the low-pressure gaseous state. However, the van der Waals model is not quantitative below

2
critical temperature. For example, an oscillative behavior that does not well reproduce the
liquid-gas phase transition and it needs to be corrected by Maxwell Construction.

6. Calculate the average translational energy of (a) one Ar molecule and (b) one mole of Ar
assuming that it is an ideal gas.

a)
Translational energy of 1mol ideal gas Ar at room temperature 298.15K:
3 3
UT  RT   8.314 JK 1mol 1  298.15K  3718.2 Jmol 1
2 2

Translational energy of 1molecule Ar gas:


3
RT
3718.2 Jmol 1
UT  2   6.174  10 21 J / molecule
NA 6.022  10 23 molecule / mol

7. Calculate the following values for He and O2. (a) the average speed <C>, (b) The root
mean squared average of speed. <C2>1/2, (c) most probable C, Cmp
in Maxwell-Bolzmann distribution. Assume that T = 400K.

a)
8 RT
average speed  C 
M
8 RT 8  8.3145 JK 1mol 1  400 K
He average speed  C    1.455 103 m  s 1
M 3
3.1415  4.003  10 Kgmol 1

8 RT 8  8.3145 JK 1mol 1  400 K


O 2 average speed  C    5.14  102 ms 1
M 3.14159  32.0  103 Kgmol 1

b)
3RT
root mean square speed  C 2 1/ 2 
M
3RT 3  8.3145 JK 1mol 1  400 K
He root mean square speed  C2 1/ 2    1.579  103 ms 1
M 4.003 103 Kgmol 1

3RT 3  8.3145 JK 1mol 1  400 K


O 2 root mean square speed  C2 1/2    5.58  102 ms 1
M 32.0 103 Kgmol 1

c)
2 RT
most probable speed C mp 
M
2 RT 2  8.3145 JK 1mol 1  300 K
He most probable speed Cmp    1.289  103 ms 1
M 4.003  103 Kgmol 1

3
2 RT 2  8.3145 JK 1mol 1  400 K
O 2 most probable speed C mp    4.559 102 ms 1
M 32.0 103 Kgmol 1

 mC 2  3
3/ 2 1/ 2
 m    8RT 
8. Prove that  C  4   0 exp  C dC gives  C    ,
 2kT   2kT   M 
where C denotes the speed of a gas molecule B that has a mass m and M is a molar mass of B.

  mC 2  3   mC 2  C 3 1   mC 2  2
 exp       
2
 C dC exp   d (C ) exp   C d (C 2 )
0
 2kT  0
 2kT  2C 2 0
 2kT 

 n!
(  x n e ax dx  )
0 a n1

1   mC 2  2 1 n! 1 1 2k 2T 2
2 0
exp 
 2kT  C d (C 2
)     
  2 a n 1 2 ( m ) 2 m2
2kT
m
(x=C2, n=1, a  )
2kT

1/ 2 1/ 2
 mC 2  3    4k 4T 4 
3/ 2 3/ 2
 m 
 C  4   

exp  
 m 
C dC  4  
2k 2T 2

 16 2 
1/ 2 m3
 3 3 3 3   
 2kT   2kT  2  k T 
2 4
0
 2kT  m  m 
1/ 2
 8(k  N ) A T 
1/ 2 1/ 2
 8kT   8 RT 
      
 m    (m  N A )   M 

9. Plot a Maxwell-Boltzmann distribution


 MC 2  2
3/2
 M 
P  C   C  4   exp   C
using Excel or other software for N2 at 250K and 750K in
 2 RT   2 RT 
0  C < 1500 m/s.

At 250K,
3/2
 MC 2  2  28.02 103 Kgmol 1   28.02 103 Kgmol 1  C 2 
3/2
 M 
C  4   exp    C  4  3.1416    exp    C2
 2 RT 
1 1 1 1
 2 RT   2  3.1416  8.314 JK mol  250 K   2  8.314 JK mol  250 K 

C  3.9493 108 exp  6.74044 106 C 2   C 2 m 1s

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At 750K,
3/2
 MC 2  2  28.02 103 Kgmol 1   28.02 103 Kgmol 1  C 2 
3/2
 M 
C  4   exp    C  4  3.1416    exp    C
2

 2 RT 
1 1 1 1
 2 RT   2  3.1416  8.314 JK mol  750 K   2  8.314 JK mol  750 K 

C  7.6004 109 exp  2.2468 106  C 2   C 2 m1s

Plot <C> vs C as following:

10. How much of the average translational energy and rotational energy do you expect for
one mole of (a) He, (b) H2O, (c) CO2, (d) NH3, (e) C6H6. Assume that T=300K.

3
Translational energy UT  nRT
2

Rotational energy Ur  nRT (diatomic & linear molecule)


3
 nRT (nonlinear molecule)
2

So, translational energy UT are the same for all substance; and rotational energy are different as list
below(n=1):

He H2O CO2 NH3 C6H6

5
3 3 3
Rotational energy 0 RT RT RT RT
2 2 2
(Ur)
0 3.7413kJ 2.4942kJ 3.7413kJ 3.7413kJ

nRT  1mol  8.314 Jmol 1 K 1  300 K  2494.2 J  2.4942kJ


11. Prove Vmc = 3b, Tc = 8a/(27bR), Pc = a/27b2 from the van der Waals equation and following
conditions at critical point:
P  RTc 2a
  0
Vm VmC  b  VmC 3
2

2P 2 RTc 6a
 0
Vm
2
VmC  b  VmC 4
3

P  RTc 2a
  0
Vm VmC  b  VmC 3
2

 RTcVmC 3  2a VmC  b  ...(1)


2

2 P 2 RTc 6a
  0
Vm VmC  b  VmC
2 3 4

 2 RTcVmC 4  6a VmC  b  ...(2)


3

Multiply 2VmC on both sides of (1)


 2VmC  RTcVmC 3  2VmC  2a VmC  b   6a VmC  b 
2 3

 2VmC  2a  6a VmC  b 
1

 2VmC  3 VmC  b 
1

 3b  VmC
Plug 3b  VmC into (1)
 RTc  3b   2a  3b  b 
3 2

 27 RTc b3  8ab 2
 27 RTc b  8a
8a
 Tc 
27 Rb
8a RT a
Plug 3b  VmC and Tc  into P   2
27 Rb Vm  b Vm

6
8a
R
a
P  27 Rb 
3b  b  3b 2
4a a
  2
b  27b 9b
a

27b 2

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