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Cowie
2. Consider a mixture of air and gasoline vapor in a cylinder with a piston. The original volume is 40.0
cm3. If the combustion of this mixture releases 950.0 J of energy to what volume will the gases expand
against a constant pressure of 650.0 torr if all the energy of combustion is converted into work to push
back the piston?
w = – PΔV
w – 950 J J 1 L atm
ΔV = – =– = 1110.8 x = 10.96 L
P 650 atm 101.3 J
atm
760
1.00 mol Fe2O3 and 2.00 mol Al are mixed at room temperature (25 °C), and a reaction is initiated. The
liberated heat is retained within the products, whose combined specific heat over a broad temperature
range is about 0.8 J g–1 °C–1. The melting point of iron is 1530 °C. Show that the quantity of heat
liberated is more than sufficient to raise the temperature of the products to the melting point of iron.
qcal 852000 J
ΔT = = = 4985 °C
mc 213.66 g 0.8 J g–1 °C–1
4. The heat of solution of KI (s) in water is +20.3 kJ/mol KI. If a quantity of KI is added to sufficient
water at 23.5 °C in a Styrofoam cup to produce 150.0 mL of 2.50 M KI, what will be the final
temperature? (Assume a density of 1.30 g/mL and a specific heat of 2.7 J g–1 °C–1 for 2.50 M KI.)
(Note that density and specific heat are significantly different from those of pure H2O for a concentrated
solution).
Find qrxn
qsol = – 7612.5 J = m c DT
qsol – 7612.5 J
ΔT = = = – 14.5 °C
mc 150.0 mL 1.30 g/mL 2.7 J g–1 °C–1
ΔT = Tf – Ti ⇒ Tf = ΔT + Ti = – 14.5 + 23.5 = 9 °C
5. A 9.00 g ice cube, initially at 0°C, is added to a cup of coffee at 363K which contains 120.0 g coffee
(liquid, not beans or powder). Assume the heat capacity of coffee is the same as water. The enthalpy of
fusion (melting) of ice is 6.0 kJ/mol. Calculate the temperature of the coffee after all the ice melts.
9.00 g H2O
= 0.500 mol H2O 363 K = 90°C
18.0 g/mol H2O
qice + qcoffee = 0
→ water
Call the final temperature of the mixture Tf. Ice will absorb heat (ΔHfus) to convert ice at 0oC to water
at 0oC, then water will warm to Tf.
J
qice = ΔHfus + mcΔT = 0.5 mol x 6000 J/mol + 9.0 g x 4.18 x (Tf – 0.00)°C
→ water g °C
J
qcoffee = 120.0 g x 4.18 x (Tf – 90.0)°C
g °C
3000 + 37.62 Tf + 501.6 Tf – 45144 = 0
539.22 Tf = 42144
Tf = 78.15°C
6. a. Can a system do work and give off heat at the same time?
a. Yes
7. The internal energy of a fixed quantity of an ideal gas depends only on its temperature. If a sample is
allowed to expand at a constant temperature (isothermal expansion): (a) Does the gas do work? (b) Does
the gas exchange heat with its surroundings? (c) What happens to the temperature of the gas? (d) What
is ΔE for the gas?
Note that combustion products are gaseous CO2 and liquid H2O
11 o
C4H6 (g) + O
2 2 (g)
→ 4 CO2 (g) + 3 H2O (l) ΔH1 = – 2540.2 kJ
13 o
C4H10 (g) + O
2 2 (g)
→ 4 CO2 (g) + 5 H2O (l) ΔH2 = – 2877.6 kJ
1 o
H2 (g) + O
2 2 (g)
→ H2O (l) ΔH3 = – 285.8 kJ
o o o o
ΔHrxn = ΔH1 + 2ΔH3 – ΔH2 = (– 2540.2) + 2 (–285.8) – (– 2877.6) = – 234.2 kJ
9. Use data from Appendix B to calculate the standard enthalpy change for the following reaction at 25°C.
Fe2O3 (s) + 3 CO (g) → 2 Fe (s) + 3 CO2 (g)
o
ΔHrxn = ∑n o
prodΔHf prod – ∑n o
reactΔHf react
o o o o o
ΔHrxn = 2 ΔHf (Fe (s)) + 3 ΔHf (CO2 (g) – ΔHf (Fe2O3 (s)) – 3 ΔHf (CO (g)) =
1
Need Cu (s) + O2 (g) → CuO (s) Reverse rxn 2 + reverse half rxn 1
2
1
Cu (s) + CuO (s) + Cu2O (s) + O2 (g) → Cu2O (s) + 2 CuO (s)
2
1
Net: Cu (s) + O2 (g) → CuO (s)
2
o 1 1
ΔHf = – ΔH2 – ΔH1 = – 11 – (288) = – 155 kJ/mol
2 2
12. Use data from Table 9.2 to estimate the enthalpy change (ΔH) for the following reaction.
H H H H
H C C H + Cl Cl H C C Cl + H––Cl
H H H H
= 657 kJ mol–1
= 770 kJ mol–1
= –113 kJ mol–1
13. Equations (1) and (2) can be combined to yield the equation for the formation of CH4 (g) from its
elements.
Use the above data and a bond energy of 436 kJ mol–1 for H2 to estimate the C–H bond energy in
methane (CH4).
ΔH = BEbroken – BEmade
14. a. Does the entropy increases or decreases when you separate a mixture of fine sand and charcoal?
b. Which has the greatest entropy, steam at 110°C, water at 25°C or ice at – 40°C?
a. Decrease A mixture has less order than its pure components, so separation ⇒ decrease in entropy.
o o o
ΔS° = 2 Sf (NH3 (g)) – Sf (N2 (g)) – 3 Sf (H2 (g)) = 2 x (193) – 192 – 3 x (131) = – 199 J mol–1 K–1
o o o
ΔH° = 2 ΔHf (NH3 (g)) – ΔHf (N2 (g)) – 3 ΔHf (H2 (g)) = 2 x (– 46) – 0 – 3 x 0 = – 92 kJ mol–1
92000 J mol–1
T< = below 462.3 K
199 J mol–1 K–1
16. The very poisonous hydrogen sulfide can be removed from natural gas (mainly methane CH4) by the
o o o o o
a. ΔGrxn = 3 ΔGf (S (s)) + 2 ΔGf (H2O (g)) – 2 ΔGf (H2S (g)) – ΔGf (SO2 (g)) =
o
ΔGrxn – 90000 J mol–1
o
ΔGrxn = – RT ln K so ln K = – =– = 36.31
RT 8.3145 J mol–1 K–1 x 298.15 K
o o o o o
b. ΔHrxn = 3 ΔHf (S (s)) + 2 ΔHf (H2O (g)) – 2 ΔHf (H2S (g)) – ΔHf (SO2 (g)) =
o o o o o
ΔSrxn = 3 Sf (S (s)) + 2 Sf (H2O (g)) – 2 Sf (H2S (g)) – Sf (SO2 (g)) =
145000 J mol–1
T< = below 780 K
186 J mol–1 K–1
o
K100 ΔHrxn 1 1 – 145000 J mol–1 1
1 –1
c. ln = – = –1 –1 x – K = – 11.756
K25 R T25 T100 8.3145 J mol K 298.15 373.15
K100
= e– 11.756
K25
17. It is quite common for a solid to change from one structure to another at a temperature below its melting
point. For example, sulfur undergoes a phase change from the rhombic crystal structure to the
monoclinic crystal at temperatures above 95°C.
ΔH < 0 and ΔS < 0 ⇒ ΔG < 0 only at low T (the +ve TΔS is smaller than –ve ΔH term)
ΔH > 0 and ΔS > 0 ⇒ ΔG < 0 only at high T (the –ve TΔS is greater than +ve ΔH term)
b. Since ΔS > 0 and systems go from ordered structure to a less ordered structure
Compare your result with the value listed in Table 13 of the CDS.
o o o
ΔSrxn = 2 Sf (F (g)) – Sf (F2 (g)) = 2 (158.8) – 202.8 = 114.8 J K–1
o o o
ΔGrxn = ΔHrxn – T ΔSrxn
o o o
ΔHrxn = ΔGrxn + T ΔSrxn = 123900 J + 298.15 K 114.8 J K–1 = 158.1 kJ/mol bonds
19. Use thermodynamic data at 298K to decide in which direction the reaction
→
H2 (g) + Cl2 (g) ← 2 HCl (g)
is spontaneous when the partial pressures of H2, Cl2 and HCl are all 0.5 atm.
o o o o
ΔGrxn = 2 ΔGf (HCl (g)) – ΔGf (H2 (g)) – ΔGf (Cl2 (g)) = 2 (– 95.30) – 0 – 0 = – 190.6 kJ
o
ΔG = ΔGrxn + RT ln Q
PHCl2 0.52
Q= = =1
PH2 PCl2 0.5 0.5
o o o
ΔG = ΔGrxn + RT ln Q = ΔGrxn + RT ln 1 = ΔGrxn = – 190.6 kJ < 0
o o o o o
At equilibrium ΔGrxn = 0 = ΔHrxn – T ΔSrxn = ΔHvap – T ΔSvap rxn is evaporation !
o
ΔHvap 104000 J mol–1
Rearrange T= = = 1147.9 K
o 90.6 J mol–1 K–1
ΔSvap