Express (∂Cp/∂P)T as a second derivative of H and find its relation to (∂H/∂P)T. (b) From the relationships found in (a), show that (∂Cp/∂V)T=0 for a perfect gas.
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(a) Express (∂Cp/∂P)T as a second derivative of H and find its relation to (∂H/∂P)T. (b) From the relationships found in (a), show that (∂Cp/∂V)T=0 for a perfect gas.
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- Since we will be dealing with partial derivatives later in the semester, this is a good opportunity to review this topic (see appendix C). Then evaluate the following partial derivatives (a) PV = nRT; (∂ P/∂V)T (b) r = (x2 + y2 + z 2 )1/2; (∂ r/∂y)x,zIndicate whether each statement is true or false. (a) Unlikeenthalpy, where we can only ever know changes in H, wecan know absolute values of S. (b) If you heat a gas suchas CO2, you will increase its degrees of translational, rotationaland vibrational motions. (c) CO2(g) and Ar(g) havenearly the same molar mass. At a given temperature, theywill have the same number of microstates.The cohesive energy density, U, is defined as U/V, where U is the mean potential energy of attraction within the sample and V its volume. Show that U = 1/2N2∫V(R)dτ where N is the number density of the molecules and V(R) is their attractive potential energy and where the integration ranges from d to infinity and over all angles. Go on to show that the cohesive energy density of a uniform distribution of molecules that interact by a van der Waals attraction of the form −C6/R6 is equal to −(2π/3)(NA2/d3M2)ρ2C6, where ρ is the mass density of the solid sample and M is the molar mass of the molecules.
- Calculate V−1(∂V/∂T)p,n for an ideal gas?The density of lead is 1.13 ✕ 104 kg/m3 at 20.0°C. Find its density (in kg/m3) at 100°C. (Use ? = 29 ✕ 10−6 (°C)−1 for the coefficient of linear expansion. Give your answer to at least four significant figures.)A sample of argon of mass 6.56 g occupies 18.5 dm3 at 305 K.(i) Calculate the work done when the gas expands isothermally against a constant external pressure of 7.7 kPa until its volume has increased by 2.5 dm3. (ii) Calculate the work that would be done if the same expansion occurred reversibly.
- Estimate the values of γ = Cp,m/CV,m for gaseous ammonia and methane. Do this calculation with and without the vibrational contribution to the energy. Which is closer to the experimental value at 25 °C? Hint: Note that Cp,m − CV,m = R for a perfect gas.(b) A sample of 4.0 mol O2 (g) is originally confined in 20 dm³ at 270 K and then undergoes adiabatic expansion against a constant pressure of 600 Torr until the volume has increased by a factor of 3.0. Calculate q, w, AT, AU and AH.Calculate the work done during the isothermal reversible expansion of a gas that satisfies the virial equation of state (eqn 1C.3b) written with the first three terms. Evaluate (a) the work for 1.0 mol Ar at 273 K (for data, see Table 1C.3) and (b) the same amount of a perfect gas. Let the expansion be from 500 cm3 to 1000 cm3 in each case.
- A sample of Ar of mass 8.30 g occupies 1.75dm3 at 330 K. (a) Calculate the work done when the gas expands isothermally against a constant external pressure of 1 bar until itsvolume has increased by 0.35 dm3 (b) Calculate the work that would be done if thesame expansion occurred reversibly(a) Write expressions for dV and dp given that V is a function of p and T and p is a function of V and T. (b) Deduce expressions for d ln V and d ln p in terms of the expansion coefficient and the isothermal compressibility.A 0.250 mol nitrogen initially at 50 °C with a volume of 8.00 L is allowed to expand reversibly and adiabatically until its volume has doubled. Calculate the value of ΔHwhen Cp = 7/2R.