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- The three normal modes of water are the symmetric stretch (3652 cm¹), the antisymmetric stretch (3756 cm¹), and the bend (1595 cm¹). (a) Calculate the molecular vibrational partition function of water at 500 K. (b) At 500 K, what fraction of water molecules have the bend excited to v₂=1. What fraction of water molecules have the symmetric stretch excited to v₁=1? Why do more molecules have the bend excited? (c) At 500 K, what fraction of water molecules have both v2-1 and v₁=1 excited?Calculate the rotational constant (B) for the molecule H12C14N, given that the H-C and C-N bond distances are 106.6 pm and 115.3 pm respectively.Consider the rotational temperatures of the following hetero diatomic molecules: θr(CO) = 2.1 K, θr(HF) = 30.2 K. In which case would the classical approximation be accurate? Justify your answer.
- The ground configuration of carbon gives rise to a triplet with the three levels 3P0, 3P1, and 3P2 at wavenumbers 0, 16.4, and 43.5 cm-1, respectively. (a) Eva luate the electronic partition function of carbon at (i) 10 K, (ii) 298 K, (b) Hence derive an expression for the electronic contribution to the molarinternal energy and plot it as a function of temperature. (c) Evaluate the expression at 25 °C.Q 1. Use the equipartition principle to estimate the value of γ = Cpm/CVm for gaseous CH3COOH. Do this calculation WITH the vibrational contribution to the energy.4. Spectroscopic measurements indicate that the rotational constants of SO2, a non-linear molecule, are 2.02736, 0.34417, and 0.29354 cm-1. Note: kg = 0.69503476 cm-1/K. (a) Compute zrot at T= 350 K assuming its symmetry number is o= 2. Hint: Using the rotational temperatures for the molecule might make this easier. (b) At what temperature would the partition function equal 2.0 × 104?
- b. The energy difference between consecutive vibrational states is 1.0 x 1020 J for a molecule. (i) Calculate the population ratio, n4/n¡, for this system at 298 K and discuss the significance of this ratio in terms of the distribution of molecules in the higher vibrational energy states. (ii) Estimate the vibrational partition function at 298 K. (iii) Estimate the fundamental vibration wave number for this molecule. h = 6.626 x 10-3ª J s k= 1.38 x 1023 J K' c = 2.998 x 10® m s''Consider the diatomic molecule AB modeled as a rigid rotor (two masses separated by a fixed distance equal to the bond length of the molecule). The rotational constant of the diatomic AB is 25.5263 cm-1. (a) What is the difference in energy, expressed in wavenumbers, between the energy levels of AB with J = 10 and J = 6? (b) Consider now a diatomic A'B', for which the atomic masses are ma 0.85 mA and mB' 0.85 mB and for its bond length ra'B' = 0.913 rAB. What is the difference in energy, expressed in wavenumbers, between the energy levels of the A'B' molecule with J = 9 and J = 7?What is the numerical value of the molecular partition function of a heteronuclear diatomic molecule given the following conditions: (i) the characteristic length is 10 nm and the volume in which the molecules are free to move is a cube with sides of 1 mm each. (ii) Only the first four rotational levels are accessible, but for some odd reason [to keep things simple] each state in each of those levels is equally populated. (iii) all molecules are in the ground vibrational state; (iv) the molecule has a triplet electronic ground level, like 02.
- The rotational constant for the molecule 1H35Cl is B = 10.60 cm-1. Using Boltzmann statistics, determine the most likely rotational state J that such a molecule would be expected to have at a temperature of 300 K.Derive an expression for the mean energy of a collection of molecules that have three energy levels at 0, ε, and 3ε with degeneracies 1, 5, and 3, respectively.The ground level of Cl is 2P3/2 and a 2P1/2 level lies 881 cm−1 above it. Calculate the electronic contribution to the heat capacity of Cl atoms at (i) 500 K and (ii) 900 K.
