Challenging Questions and Their Answers
Here are some challenging questions on the Van der Waals equation, including their answers:
Question 1: Calculate the critical temperature, critical pressure, and critical volume for nitrogen
gas using the Van der Waals constants a=1.39 L2atm/mol2a = 1.39 \,
\text{L}^2\text{atm/mol}^2a=1.39L2atm/mol2 and b=0.0391 L/molb = 0.0391 \,
\text{L/mol}b=0.0391L/mol.
Solution:
1. Critical Temperature TcT_cTc: Tc=8a27RbT_c = \frac{8a}{27Rb}Tc=27Rb8a
Tc=8×1.3927×0.0821×0.0391T_c = \frac{8 \times 1.39}{27 \times 0.0821 \times
0.0391}Tc=27×0.0821×0.03918×1.39 Tc≈126.2 KT_c \approx 126.2 \, \text{K}Tc
≈126.2K
2. Critical Pressure PcP_cPc: Pc=a27b2P_c = \frac{a}{27b^2}Pc=27b2a
Pc=1.3927×(0.0391)2P_c = \frac{1.39}{27 \times (0.0391)^2}Pc=27×(0.0391)21.39
Pc≈3.39 atmP_c \approx 3.39 \, \text{atm}Pc≈3.39atm
3. Critical Volume VcV_cVc: Vc=3bV_c = 3bVc=3b Vc=3×0.0391V_c = 3 \times
0.0391Vc=3×0.0391 Vc≈0.1173 L/molV_c \approx 0.1173 \,
\text{L/mol}Vc≈0.1173L/mol
Question 2: A 5.0 L container holds 2 moles of ammonia gas at 298 K. Calculate the pressure of
the gas using both the Ideal Gas Law and the Van der Waals equation. The constants for
NH3NH_3NH3 are a=4.17 L2atm/mol2a = 4.17 \,
\text{L}^2\text{atm/mol}^2a=4.17L2atm/mol2 and b=0.0371 L/molb = 0.0371 \,
\text{L/mol}b=0.0371L/mol.
Solution:
1. Ideal Gas Law: PV=nRTPV = nRTPV=nRT P=nRTVP = \frac{nRT}{V}P=VnRT
P=2×0.0821×2985.0P = \frac{2 \times 0.0821 \times 298}{5.0}P=5.02×0.0821×298
P≈9.8 atmP \approx 9.8 \, \text{atm}P≈9.8atm
2. Van der Waals Equation:
o Calculate molar volume (VmV_mVm): Vm=Vn=5.02=2.5 L/molV_m = \frac{V}
{n} = \frac{5.0}{2} = 2.5 \, \text{L/mol}Vm=nV=25.0=2.5L/mol
o Substitute into Van der Waals equation: (P+4.172.52)(2.5−0.0371)=0.0821×298\
left( P + \frac{4.17}{2.5^2} \right) (2.5 - 0.0371) = 0.0821 \times 298(P+2.524.17
)(2.5−0.0371)=0.0821×298 (P+0.668)(2.4629)=24.4758\left( P + 0.668 \right)
(2.4629) = 24.4758(P+0.668)(2.4629)=24.4758 P+0.668=24.47582.4629P +
0.668 = \frac{24.4758}{2.4629}P+0.668=2.462924.4758 P+0.668≈9.94P + 0.668
\approx 9.94P+0.668≈9.94 P≈9.27 atmP \approx 9.27 \, \text{atm}P≈9.27atm
Question 3: For a gas with Van der Waals constants a=2.49 L2atm/mol2a = 2.49 \, \text{L}^2\
text{atm/mol}^2a=2.49L2atm/mol2 and b=0.0427 L/molb = 0.0427 \,
\text{L/mol}b=0.0427L/mol, determine the molar volume at 300 K and 50 atm using the Van der
Waals equation.
Solution:
Given: P=50 atmP = 50 \, \text{atm}P=50atm, T=300 KT = 300 \, \text{K}T=300K,
a=2.49 L2atm/mol2a = 2.49 \, \text{L}^2\text{atm/mol}^2a=2.49L2atm/mol2, b=0.0427
L/molb = 0.0427 \, \text{L/mol}b=0.0427L/mol.
Substitute and solve: (50+2.49Vm2)(Vm−0.0427)=0.0821×300\left( 50 + \frac{2.49}
{V_m^2} \right) (V_m - 0.0427) = 0.0821 \times 300(50+Vm22.49)(Vm
−0.0427)=0.0821×300 (50+2.49Vm2)(Vm−0.0427)=24.63\left( 50 + \frac{2.49}
{V_m^2} \right) (V_m - 0.0427) = 24.63(50+Vm22.49)(Vm−0.0427)=24.63
This results in a cubic equation in VmV_mVm:
50Vm−50×0.0427+2.49Vm−2.49×0.0427Vm2=24.6350V_m - 50 \times 0.0427 + \frac{2.49}
{V_m} - \frac{2.49 \times 0.0427}{V_m^2} = 24.6350Vm−50×0.0427+Vm2.49−Vm2
2.49×0.0427=24.63
Solving this cubic equation for VmV_mVm requires numerical methods, such as the Newton-
Raphson method, or using computational tools.
Numerical Solution (approximation): Let's assume an initial guess for VmV_mVm and refine
it:
1. Initial Guess: Vm≈0.5 L/molV_m \approx 0.5 \, \text{L/mol}Vm≈0.5L/mol
2. Iterate using numerical method or solver to refine VmV_mVm:
Using an iterative solver, we can find: Vm≈0.492 L/molV_m \approx 0.492 \, \text{L/mol}Vm
≈0.492L/mol
Question 4: Compare the pressures calculated using the Ideal Gas Law and the Van der Waals
equation for 1 mole of hydrogen gas (H2H_2H2) at 273 K in a 1 L container. The constants for
H2H_2H2 are a=0.244 L2atm/mol2a = 0.244 \, \text{L}^2\text{atm/mol}^2a=0.244L2atm/mol2
and b=0.0266 L/molb = 0.0266 \, \text{L/mol}b=0.0266L/mol.
Solution:
1. Ideal Gas Law: P=nRTVP = \frac{nRT}{V}P=VnRT P=1×0.0821×2731P = \frac{1 \
times 0.0821 \times 273}{1}P=11×0.0821×273 P≈22.4 atmP \approx 22.4 \, \
text{atm}P≈22.4atm
2. Van der Waals Equation:
o Calculate molar volume (VmV_mVm): Vm=Vn=11=1 L/molV_m = \frac{V}{n}
= \frac{1}{1} = 1 \, \text{L/mol}Vm=nV=11=1L/mol
o Substitute into Van der Waals equation: (P+0.24412)(1−0.0266)=0.0821×273\
left( P + \frac{0.244}{1^2} \right) (1 - 0.0266) = 0.0821 \times 273(P+120.244)
(1−0.0266)=0.0821×273 (P+0.244)(0.9734)=22.4133\left( P + 0.244 \right)
(0.9734) = 22.4133(P+0.244)(0.9734)=22.4133 P+0.244=22.41330.9734P +
0.244 = \frac{22.4133}{0.9734}P+0.244=0.973422.4133 P+0.244≈23.03P +
0.244 \approx 23.03P+0.244≈23.03 P≈22.79 atmP \approx 22.79 \, \
text{atm}P≈22.79atm
These challenging problems and their solutions illustrate the application of the Van der Waals
equation and highlight the differences between real and ideal gas behavior.
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