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Chemistry 331 In Class Exercise Review for Final #1) (a) What are the different ways in which energy can be distributed in a molecule (degrees of freedom)? (b) How can part (a) be treated in terms of simple quantum mechanics (be specific)? (c) How can part (a) be treated experimentally (be specific)? #2) What is the scientific basis for the absolute temperature scale? #3) Below is a graph of compressibility vs. pressure for a number of real gases: Which gas has the largest attractive force and which gas has the largest repulsive force and why? Chemistry 331 In Class Exercise Review for Final #4) What is the law of corresponding states and why it important when describing real gases in terms of cubic equations of state? #5) Name three common attractive forces in molecular systems (the so called they be used to determine the second viral coefficient (use words only). #6) The van der Waal’s equation is given below: P= RT a − 2 (V − b) V Give a physical interpretation of what the parameter a and b account for. #7) State the first law of thermodynamics. #8) State the second law of thermodynamics. #9) State the third law of thermodynamic. 1 r6 forces) and how can Chemistry 331 In Class Exercise Review for Final #10) Give an example, an observation, in which the first law of thermodynamics applies. #11) Give an example, an observation, in which the second law of thermodynamics applies. #12) What is the difference between system and surroundings. #13) Using a reversible cyclic process as your example, explain why work is not a state function. #14) Heat and work are two common ways in which energy is _____________. #15) Describe what work is in terms of extending a spring. If the spring is the system, is the work positive or negative? #16) In molecular terms what is heat capacity. #17) What is the difference between a reversible and irreversible process? Give examples of both. Chemistry 331 In Class Exercise Review for Final #18) Given a system that contains an ideal gas, how would you describe the state of the system? #19) True or False: (q+w) is not a state function. #20) True or False: The ideal gas equation is an example of an equation of state. #21) True or False: If a system undergoes a cyclic process ΔH ≠ 0. #22) For the process below, how would one calculate ΔH? #23) Define the what the following paths mean. a) Isobaric b) Isothermal c) Isochoric d) Adiabatic e) Cyclic #24) The change in Enthalpy at constant pressure is equal to ___________ and the change in Internal Energy is equal to ___________ at constant volume. #25) If a chemical reaction releases heat into the environment it is call ______________ and if the chemical reaction absorbs heat from the environment it is called _____________. Chemistry 331 In Class Exercise Review for Final #26) What is Hess’s Law? #27) Using pictures and words describe the isothermal compression of an ideal gas in which a minimum amount of work has been done on the system. #28) Using words and equations give a detailed explanation of what heat and work is from a molecular point of view (statistical). #29) A monatomic ideal gas will cool as it undergoes an adiabatic expansion. Why? Chemistry 331 In Class Exercise Review for Final #30) Use molecular ideas (ie. S = k ln(N) ) to describe the nature of entropy. #31) In terms of the change in Gibbs free energy, when is a chemical process spontaneous, nonspontaneous, and when does it reach equilibrium? #32) Given that dG = VdP – SdT, derive the expression d G ( T ) = − H . This is the Gibbs-Helmholtz dT T2 equation and it describes how the Gibbs Free energy changes with temperature at constant pressure. Chemistry 331 In Class Exercise Review for Final #33) Find the Maxwell relation that comes for a consideration of Gibbs Free Energy. #34) Which has the greater molar entropy under the same conditions; CO or CO2. Justify your answer. #35) Arrange the following reactions according to increasing values of ΔSReaction. (a) (b) (c) (d) S(s) + O2(g) → SO2(g) H2(g) + O2(g) → H2O2(l) CO(g) + 3H2(g) → CH4(g) + H2O(l) C(s) + H2O(g) → CO(g) + H2(g) #36) For a non-isolated system Helmoltz and Gibbs Energy can be used to predict whether a processes is spontaneous or not. Why is this true? Chemistry 331 In Class Exercise Review for Final #37) Write dU, dH, dA and dG in terms of their natural and independent variables. #38) What is fugacity and why is it useful? #39) Sketch a Solid-Liquid-Gas pressure vs. volume phase diagram and indicate the regions in which µgas = µsolid, µgas = µliquid, µliquid = µsolid and µgas = µliquid = µsolid. #40) In terms of dG, µliquid, and µgas, describe the conditions in which vaporization is a spontaneous process. Chemistry 331 In Class Exercise Review for Final #41) For ideal solutions mixing is always spontaneous while this is not so for non-ideal solutions. Why? #42) Why is the equilibrium constant for a chemical reaction dependent on temperature only? #43) What is Le Chateliers Principle? #44) Indicate on the diagram below the range for the extent of reaction in which the forward reaction is spontaneous. Chemistry 331 In Class Exercise Review for Final #45) In terms of chemical potentials what is the condition for the following reaction to be spontaneous in the forward direction. aA + bB ↔ cC + dD #46) Derive an expression for ΔGmix for the mixing of two ideal gases. #47) Knowing that ΔG = RT ln Q for a chemical reaction, where Q is the reaction quotient and K is the K equilibrium constant, when does the reaction come to equilibrium, when is the reaction spontaneous, and when is the reaction non-spontaneous. Give your answers in terms of K and Q. Chemistry 331 In Class Exercise Review for Final #48) The van’t Hoff equation is an expression that gives the temperature dependence of the equilibrium constant. The vant’ Hoff equation is: ⎛K ⎞ ΔH o ⎛ 1 1 ⎞ ln ⎜ 2 ⎟ = − ⎜ − ⎟ R ⎝ T2 T1 ⎠ ⎝ K1 ⎠ Using this information describe how you could determine whether a chemical reaction is endothermic o o o or exothermic and how you can extract ΔH , ΔS , and ΔG ? #49) Given the phase diagram below, label each line and indicate which are described by the Claperyon equation and and which are described by the Clausius-Claperyon Equation and why. #50) On the curve below circle and label the part of the curve that obeys Raoult’s law and the part that obeys Henry’s law.