CH301 Fall 2008 Worksheet 12 Answer Key

1. Assume we want to use a bomb calorimeter to determine the specific heat capacity of an
unknown liquid. We use 3 L of the unkown liquid and perform a known reaction that
releases 400 kJ of heat. We measure an initial and final temperature of 25 ºC and 28.7 ºC,
-1
respectively. If the heat capacity of the calorimeter is 85 J·K , and the density of the liquid
-1
is 2.34 g·mL , what is the specific heat capacity of the unknown liquid?
ΔH = 400 kJ
-1 -1
m = 3 L * 1000 mL·L * 2.34 g·mL = 7020 g
ΔT = Tf - Ti = 28.7 ºC - 25 ºC = 3.7 ºC = 3.7 K
-1 -1 -1
ccal = 85 J·K * .001 kJ·J = 0.085 kJ·K
ΔH = m·c·ΔT + ccal·ΔT
c = (ΔH - ccal·ΔT)/(m·ΔT)
-1
= (400 kJ - 0.085 kJ·K * 3.7 K)/(7020 g * 3.7 K)
-1 -1 -1 -1
= 0.01539 kJ·g ·K = 15.39 J·g ·K

2. Lets say we filled the calorimeter above with 3 L of water and performed the same known
reaction above. We measured a final temperature of 57.56 ºC, but forgot to measure the
-1
inital temperature. Considering the density and specific heat capacity of water are 1 g·mL
-1 -1
and 4.184 J·g ·K , could we calculate what the initial temperature must have been? If so,
what was the initial temperature?
Yes, we can determine Ti. We don't know the value of either ΔT or Ti, so we have two
unknowns, but we also have two equation, so we can solve:
ΔH = m·c·ΔT + ccal·ΔT and ΔT = Tf - Ti
-1 -1 -1
ΔT = ΔH/(m·c + ccal) = 400,000 J/(3000 g * 4.184 J·g ·K + 85 J·K )
= 32.34 K = 32.34 ºC
Ti = Tf - ΔT = 57.56 ºC - 32.34 ºC = 25.22 ºC

3. Given the following data:

-1
P4(s) + 6Cl2(g) ↔ 4PCl3(g) ΔH = -1,225.6 kJ·mol
-1
P4(s) + 5O2(g) ↔ P4O10(s) ΔH = -2,967.3 kJ·mol
-1
PCl3(g) + Cl2(g) ↔ PCl5(g) ΔH = -84.2 kJ·mol
-1
PCl3(g) + 1/2O2(g) ↔ Cl3PO(g) ΔH = -285.7 kJ·mol
calculate ΔH for the reaction
P4O10(s) + 6PCl5(g) ↔ 10Cl3PO(g)
-1 -1 -1
ΔHrxn = (1 * -1,225.6 kJ·mol ) + (-1 * -2,967.3 kJ·mol ) + (-6 * -84.2 kJ·mol ) + (10
-1
* -285.7 kJ·mol )
-1
= -610.1 kJ·mol

4. Given the following data:

-1
2O3(g) ↔ 3O2(g) ΔH = -427 kJ·mol
-1
O2(g) ↔ 2O(g) ΔH = 495 kJ·mol
-1
NO(g) + O3(g) ↔ NO2(g) + O2(g) ΔH = -199 kJ·mol
calculate ΔH for the reaction
NO(g) + O(g) ↔ NO2(g)
-1 -1 -1
ΔHrxn = (-1/2*-427 kJ·mol ) + (-1/2*495 kJ·mol ) + (1*-199 kJ·mol )
-1
= -233 kJ·mol

5. Hyrdoiodic acid (HI) and sodium hydroxide (NaOH) are a strong acid and strong base
respectively. Calculate the change in enthalpy for their neutralization reaction:
HI(g) + NaOH(s) → NaI(s) and H2O(l)
Consult Appendix 2 in your ebook for standard enthalpy of formation values.
ΔHrxn = ΣHf,products - ΣHf,reactants
-1 -1 -1 -1
= (-287.78 kJ·mol + -285.83 kJ·mol ) - (26.48 kJ·mol + -425.61 kJ·mol )
-1
= -174.48 kJ·mol
6. Calculate the change in enthalpy for the reaction of hydroxylamine and hydrogen
peroxide to form ammonia, water and ozone.
2NH2OH(s)2 + H2O2(aq) → 2NH3(aq) + H2O(l) + O3(g)
Consult Appendix 2 in your ebook for standard enthalpy of formation values.
ΔHrxn = ΣHf,products - ΣHf,reactants
-1 -1 -1 -1
= (2*-80.29 kJ·mol + -285.83 kJ·mol + 142.7 kJ·mol ) - (2*-114.2 kJ·mol +
-1
-191.17 kJ·mol )
-1
= 115.86 kJ·mol

7. Using bond enthalpies, approximate the change in enthalpy for the reaction in question 6
above. Would the reaction be more or less endothermic with every species in the gas
phase? Consult tables 6.7 and 6.8 in your ebook for mean bond enthalpies
ΔHrxn = ΣBEreactants - ΣBEproducts
= (2*N-H + N-O + 3*O-H + O-O) - (3*N-H + 2*O-H + O-O + O=O)
-1 -1 -1 -1 -1
= (2*388 kJ·mol + 210 kJ·mol + 3*463 kJ·mol + 157 kJ·mol ) - (3*388 kJ·mol +
-1 -1 -1
2*463 kJ·mol + 157 kJ·mol +496 kJ·mol )
-1
= -211 kJ·mol
The reaction would be less endothermic in the gas phase; it would in fact be exothermic.

8. Calculate the change in standard molar entropy for the reaction in question 6 above.
Consult Appendix 2 in your ebook for standard molar entropy values. Assume that
hydroxyalmine has a standard molar entropy of 0. Also, discuss whether we are
overestimating or underestimating the change in standard molar entropy for the reaction .
ΔSrxn = ΣSm,products - ΣSm,reactants
-1 -1 -1 -1 -1 -1 -1 -1
= (2*111.3 J·mol ·K + 69.91 J·mol ·K + 238.93 J·mol ·K ) - (143.9 J·mol ·K )
-1 -1
= 387.54 J·mol ·K
By assuming that a reactant has no entropy, we are overestimating ΔS rxn.

9. Based on the values of ΔHrxn and ΔSrxn calculated in question 6 and question 8, how
would the reactions spontaneity be effected by temperature? Explain your answer.
The reaction would become more spontaneous as temperature increases. Based on the
Maxwell free energy equation, ΔGrxn = ΔHrxn + TΔSrxn, and the convention that a negative
free energy corresponds to a spontaneous process, we can state that in spite of the change
in enthalpy being positive (non-spontaneous), if the temperature is sufficiently high, then
the change in entropy (also positive, i.e spontaneous) can drive the reaction and make it
spontaneous.

10. Based on the values of ΔHrxn and ΔSrxn calculated in question 6 and question 8, at what
temperature would the reaction switch from being non-spontaneous to spontaneous. In
other words, what would T be if ΔGrxn = 0. Considering your answer to number 8, are we
overestimating or underestimating the temperature at which the reaction switches from
non-spontaneous to spontaneous?
ΔGrxn = ΔHrxn - TΔSrxn = 0
-1 -1 -1
T = ΔHrxn/ΔSrxn = 115,860 kJ·mol /387.54 J·mol ·K = 299 K
Because the equilibrium temperature is inversely proportional to ΔS rxn, overestimating
ΔSrxn would mean underestimating T.

11. In the list of elements below, mark (circle, underline, etc.) all of the elements that are
not shown in their standard state.
Cdiamond(s) Ca(s) B2(s) Na(s) Fe(s) Hg(s)
Br2(l) Mo(s) H(g) He(g) Xe(g) Rb2(s)
Cd(l) As(s) N2(l) O2(l) Si60(s) F2(g)
12. Write the standard formation reactions for the following chemical species
NH3(g)
1/2N2(g) + 3/2H2(g) → NH3(g)
Fe2O3(s)
2Fe(s) + 3/2O2(g) → Fe2O3(s)
O2(l)
O2(g) → O2(l)
O3(g)
3/2O2(g) → O3(g)
NH2OH(s)
1/2N2 + 3/2H2 + 1/2O2 → NH2OH(s)

13. State in your own words the first law of thermodynamics. What are some of the
consequences of the first law?
The energy of the universe is a constant. Some important consequences are that the
energy of a system can be increased or decreased by adding/subtracting heat or doing work
on/by the system. Etc...

14. What is a state function? List all of the state functions you can.
A state function is a parameter or value of a system that depends only on the state of the
system (whence the name), and not on how the system arrived at that state. Etc...
Temperature, pressure, volume, density, enthalpy, entropy, Gibbs free energy, Helmholz
free energy, fugacity, internal energy, mass, chemical potential, number of moles etc...

15. If we were harnessing a combustion reaction that produces lots of gaseous products to
do work (like in a car's engine), how would lowering the temperature effect the amount of
work we could do?
Because w = -ΔngasRT, as we lower T we also decrease the amount of work we can do.
In other words, work done by expanding gases is directly proportional to the temperature.

Consider the following molecules for questions 16-20: O 3, N2, CH4, SF6
16. Which has the fewest rotational modes? how many? why?
N2 has the fewest because it is linear (2 rotational modes) rather than non-linear (3
rotational modes).

17. Which has most vibrational modes? how many? why?

SF6 has the most rotational modes because it has 3*7 = 21 total modes, and 6 of those
are rotational and translation, leaving 15 vibrational modes.

18. Do any have more or less than 3 translational modes? why?

No, all molecules have 3 translational modes.

19. Which has the most total modes? how many? why?
SF6 has the most total modes, because total modes is equal to three times the number of
atoms, 21 in this case.

20. Which has 9 vibrational modes?

CH4 has 15 total modes minus 3 translational and 3 rotational, leaving 9 vibrational
modes.