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tanarmadillo181Lv1

15 Apr 2020

Indicate whether each statement is true or false. (a) The third law of thermodynamics says that the entropy of a perfect, pure crystal at absolute zero increases with the mass of the crystal. (b) “Translational motion” of molecules refers to their change in spatial location as a function of time. (c) “Rotational” and “vibrational” motions contribute to the entropy in atomic gases like He and Xe. (d) The larger the number of atoms in a molecule, the more degrees of freedom of rotational and vibrational motion it likely has.

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Casey DurganLv2

22 May 2020

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Qualitative Predictions about Entropy Entropy is the randomness of a system. At the molecular level, entropy can be described in terms of the possible number of different arrangements of particle positions and energies, called microstates. The more microstates the system has, the greater its entropy. Microstates depend on molecular motion. Molecules may undergo three different types of motion: translational motion, vibrational motion, and rotational motion. During translational motion, the entire molecule moves in one direction. During vibrational motion, atoms in a molecule move toward and away from one another. During rotational motion, molecules rotate or spin. The number of molecules, the space available for the molecules, and the energy available to the molecules will impact the number of microstates. Another way of looking at entropy is that the universe is moving toward a broader distribution of energy. The universe has a constant amount of energy as stated in the first law of thermodynamics. The universe started with low entropy (concentrated in the moment before the "big bang") and the entropy has since been constantly increasing by distributing this energy. Heat distribution from high temperature to low temperature is a another example of this phenomenon. Part A Rank these systems in order of decreasing entropy. Rank from highest to lowest entropy. To rank items as equivalent, overlap them. Hints HelpReset Least entropyGreatest entropy 1 mol of neon gas at 273 K and 40 L 1 mol of chlorine gas at 273 K and 40 L 1 mol of hydrogen peroxide gas at 273 K and 40 L 1 mol of neon gas at 273 K and 20 L 1/2 mol of neon gas at 273 K and 20 L 1/2 mol of neon gas at 100 K and 20 L 1/2 mol of liquid neon at 100 K The correct ranking cannot be determined. SubmitMy AnswersGive Up Incorrect; Try Again; 4 attempts r

For which system below would quantum effects be leastnoticeable?

-The collision of two N₂ molecules in a gas, whichchanges the rotational energy of both

-Polarization of the electron density of ethanol resulting inexcitation of vibrational motions

-An electron-sized particle moving in a 1 m³ box asthe temperature decreases by 10 degrees

-A hydrogen atom being struck by a UV photon

We have dealt with two different ensembles, canonical andmicrocanonical. Which of the following statements is inaccurateregarding these ensembles?

-The canonical ensemble is always considered as a subset of alarger reservoir, which acts as the surroundings.

-The microcanonical ensemble is defined to have constant energy,volume, and composition.

-The microcanonical ensemble is a smaller subset of microstatesof the canonical ensemble.

-The canonical ensemble is generally more useful than themicrocanonical for chemical processes.

Which statement below is most correct regarding the partitionfunction of an ensemble?

-For a given temperature, the high-energy contributions to thepartition function are more heavily weighted.

-Once a partition function is defined in a specific ensemble, itis valid in all other ensembles.

-It tells us the numerical order of the energy levels for agiven system.

-It provides a measure of the energy levels available to asystem at a given temperature.

Consider a cup-carrier from your favorite take-out restaurant.The carrier can hold four cups, and you have to place two cups (onelarge, one small) into the carrier, with no preference forposition. How many microstates can you form with two cups in thefour spaces?

-12

-8

-16

-6

Boltzmann's definition of the entropy was a breakthrough inunderstanding statistical thermodynamics. What is the bestdefinition of Boltzmann's entropy?

-The Boltzmann entropy is a count of the total distinctmicrostates in a system.

-The Boltzmann entropy is a measure of the randomness of anensemble.

-The Boltzmann entropy is a count of the accessible energylevels at a given temperature.

-The Boltzmann entropy is a measure of the useful work availablein an ensemble.

Our canonical ensemble was defined such that the temperature,volume, and number of particles were each held constant. In termsof the Legendre transform, which thermodynamic potential isfundamental in the canonical ensemble?

-The Helmholtz energy

-The internal energy

-The Gibbs energy

-The enthalpy

The equipartition principle can be used to estimate the constantvolume heat capacities of gases. Under which circumstances wouldthe full equipartition heat capacity most closelyapproximate the measured value of C_V?

-A sample of N₂ gas at 373K

-A sample of propane gas (C₃H₈) at roomtemperature

-A sample of water vapor at 373K

-A sample of Br₂ vapor at room temperature

Which factor below does not contribute to the rotationalpartition function of a molecule?

-The rotational quantum number

-The nuclear and electronic spin states

-The rotational constant(s)

-The temperature of the molecule

We were able to reduce the vibrational partition function froman infinite series to a function of a single exponential, but onlyapproximately. Which approximation below was NOT used?

-We assumed that the vibrational energy can be expressed asv?_e.

-We assumed that the energy levels were close enough to allowintegration instead of summation.

-We assumed that the vibrational motion is purely harmonic.

-We assumed that the separations are relatively small, due tohigh temperature or lower vibrational constant.

The derived partition function for an ideal gas depends on allof the physical parameters listed below except for which one?

-Molecular symmetry

-The temperature of the molecules

-The volume of the sample

-Mass of the molecules

Deriving the translational partition function is more involvedthan deriving the rotational and vibrational partition functions.Which statement below is NOT a reason for this?

-There are so many possible translational energy levels, thatthe integral does not converge to a finite value.

-The integral of translational states for a single particle mustbe taken over a 6-dimensional hypervolume.

-The degeneracy of translational states is not obvious becausethey lie so close in energy.

-Translational degrees of freedom involve interactions betweenall molecules in the sample, whereas rotations and vibrations donot.

The connection between the Equipartition Principle and thetranslational partition functions helped to demonstrate that thetemperature of a system depends on the easily excited degrees offreedom. Why should this be true?

-In systems with easily excited degrees of freedom, a change inthe entropy requires energy changes on the order of thermalenergy.

-In systems with easily excited degrees of freedom, smallincreases in the pressure make excited states more accessible,

increasing the temperature.

-In systems with easily excited degrees of freedom, thepotential energy is no longer dependent on the temperature of thesystem.

-In systems with easily excited degrees of freedom, thermalenergy is sufficient to allow one to treat the energy levels as acontinuum.

The connection between the Maxwell-Boltzmann distribution andthe translational partition function allowed us to betterunderstand the distribution of speeds. Which statement below is NOTa consequence of the translational partition function?

-The population of the lowest speeds is very small.

-The pressure of the gas increases as the velocityincreases.

-An increase in the temperature will result in shifting thedistribution to higher energies.

-The population of the highest speeds is very small.

When dealing with quantum energy levels, there are severalimportant factors to consider. Which concept below is NOT importantto quantum energy levels?

-The set of quantum numbers

-Degeneracy

-The deBroglie wavelength

-The ground state

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