Chapter 4: Thermochemistry

Q4.1) Under what conditions are H and U for a reaction involving gases and/or liquids or solids identical? H = U + (p V). H U for reactions involving liquids and solids, since, in a good approximation, the volume does not change in a chemical reaction. On the other hand, for chemical reactions involving gases, (p V) = n R T, and H U if the number of moles of reactants and products is identical. Q4.2) If the H f for the chemical compounds involved in a reaction are available at a given temperature, how can the reaction enthalpy be calculated at another temperature? The accurate calculation of the reaction enthalpy at another temperature requires the knowledge of the heat capacities of all reactants and products:
T

H o = H o K + T 298.15

298.15 K

C (T ) dT
p

For similar heat capacities of reactants and products, the reaction enthalpy does not vary significantly over a limited temperature range. Q4.3) Does the enthalpy of formation of compounds containing a certain element change if the enthalpy of formation of the element under standard state conditions is set equal to 100 kJ mol1 rather than to zero? If it changes, how will it change for the compound AnBm if the formation enthalpy of element A is set equal to 100 kJ mol1? Yes, because part of the enthalpy change of the reaction will be attributed to the element. For the reaction n A + m B AnBm:
o o o H o reaction = H f (A n B m ) n H f (A ) m H f (B) o o H o (A n B m ) = H o f reaction + n H f (A ) + m H f (B )

Therefore, H o (A n Bm ) for the compound will increase by 100 n kJ mol-1. f

Q4.4) Is the enthalpy for breaking the first CH bond in methane equal to the average CH bond enthalpy in this molecule? Explain your answer.

No. The average bond enthalpy is the average of enthalpies for the four steps leading to a complete dissociation. The enthalpy of each successive dissociation step will increase.
Q4.5) Why is it valid to add the enthalpies of any sequence of reactions to obtain the enthalpy of the reaction that is the sum of the individual reactions?

Since H is a state function, it does not depend on the path of the reaction. It has the same value regardless of how many intermediate steps are involved in the reaction.
Q4.6) The reactants in the reaction 2NO(g) + O2(g) 2NO2(g) are initially at 298 K. Why is the reaction enthalpy the same if the reaction is (a) constantly kept at 298 K or (b) if the reaction temperature is not controlled and the heat flow to the surroundings is measured only after the temperature of the products is returned to 298 K?

The reaction enthalpy is the same since DH is a state function and does not depend on the path.
Q4.7) In calculating H reaction at 298.15 K, only the H f of the compounds that take part in

the reactions listed in Tables 4.1 and 4.2 (Appendix B, Data Tables) are needed. Is this statement also true if you want to calculate H reaction at 500 K? No. At any temperature other than 298.25 K, the heat capacities of all elements and compounds that appear in the overall reaction enter into the calculation.
Q4.8) What is the point of having an outer water bath in a bomb calorimeter (see Figure 4.3), especially if its temperature is always equal to that of the inner water bath?

This water bath effectively isolates the calorimeter and the inner water bath from the rest of the universe. Because the temperatures of the water baths are the same, there is no heat follow between them. Because the container of the inner water bath has rigid walls, no work is done on the composite system consisting of the calorimeter and the inner water bath. Therefore, the calorimeter and the inner water bath form an isolated system.
Q4.9) What is the advantage of a differential scanning calorimeter over a bomb calorimeter in determining the enthalpy of fusion of a series of samples?

All samples can be measured in parallel, rather than sequentially. This reduces both the measurement time, and the possibility of errors.
Q4.10) You wish to measure the heat of solution of NaCl in water. Would the calorimetric technique of choice be at constant pressure or constant volume? Why?

Constant pressure calorimetry is the technique of choice because none of the reactants or products is gaseous, and it is therefore not necessary to contain the reaction. Constant pressure calorimetry is much easier to carry out than constant volume calorimertry.

Chapter 5: Entropy and the Second and Third Laws of Thermodynamics

Q5.1) Which of the following processes is spontaneous? a. The reversible isothermal expansion of an ideal gas b. The vaporization of superheated water at 102C and 1 bar c. The constant pressure melting of ice at its normal freezing point by the addition of an infinitesimal quantity of heat d. The adiabatic expansion of a gas into a vacuum

a) is not spontaneous because the system and surroundings are at equilibrium. b) is spontaneous because the equilibrium phase under the conditions given is a gas. c) is not spontaneous because the process is reversible. d) is spontaneous because at equilibrium, the density of a gas is uniform throughout its container.
Q5.2) Why are Sfusion and Svaporization always positive?

This is the case because fusion and vaporization always. In each of the transitions, attractive forces must be overcome.
Q5.3) Why is the efficiency of a Carnot heat engine the upper bound to the efficiency of an internal combustion engine?

This is the case because the maximum work that can be done on the surroundings in the expansion of a gas is a reversible process.
Q5.4) The amplitude of a pendulum consisting of a mass on a long wire is initially adjusted to have a very small value. The amplitude is found to decrease slowly with time. Is this process reversible? Would the process be reversible if the amplitude did not decrease with time?

No, because dissipative forces are acting on the system. If the amplitude did not decrease, no dispersive forces act on the system and the oscillation is reversible in the limit of very small amplitudes.
Q5.5) A process involving an ideal gas is carried out in which the temperature changes at constant volume. For a fixed value of T, the mass of the gas is doubled. The process is repeated with the same initial mass and T is doubled. For which of these processes is S greater? Why?

S is greater if the mass is doubled, because S increases linearly with the amount of material. By contrast, S only increases as the logarithm of the temperature. This increase is much slower than a linear increase.
Q5.6) Under what conditions does the equality S = H/T hold?

Because S =

dq reversible , the equality holds if dq reversible = H . This is the case for a reversible T process at constant pressure.

Q5.7) Under what conditions is S < 0 for a spontaneous process?

For a spontaneous process, S + Ssurroundings < 0 . The inequality S < 0 is satisfied only if Ssurroundings > 0 and Ssurroundings > S .
Q5.8) Is the equation
Tf

S =

Ti

CV T

Vf

dT +

Vi

dV = CV ln

Tf Ti

V Vi f

valid for an ideal gas? No. Because and are not independent of V for an ideal gas, they cant be taken out of the integral.
Q5.9) Without using equations, explain why S for a liquid or solid is dominated by the temperature dependence of S as both P and T change.

It is useful to think of S = S (V,T). Because V changes very little with p for a liquid or solid, entropy changes are dominated by changes in T rather p for liquids and solids.
Q5.10) You are told that S = 0 for a process in which the system is coupled to its surroundings. Can you conclude that the process is reversible? Justify your answer.

No. The criterion for reversibility is S + Ssurroundings = 0 . To decide if this criterion is satisfied, Ssurroundings must be known.