Thermo - Part I

Extra Problems to Try (page 7)

Problem 1:
50.0 mL dilute AgNO3 is added to a solution with OH– ions in a coffee cup calorimeter. Ag2O
precipitates and the temperature of the liquid goes from 23.78 to 25.19°C. Assume that the mixture has
the same specific heat as water. Calculate "qsurr" for a mass of 150. g. Is the reaction exothermic or
endothermic?
Solution: qSurroundings = mass × specific heat × change in temp
qSurroundings = 150. g × 4.184 J/g⋅ºC × (25.19 - 23.78 ºC)
qSurroundings = 885 Joules
Rxn exothermic (T of mixture rose; ∴rxn released heat to its surroundings).

Problem 2:
A 48.9 sample of metal at 95.72°C is added to 43.58 g water at 23.84°C. The final temperature of the
(metal + water) is 28.37°C. What is the specific heat of the metal in J/(g deg)?
Solution: Heat transfer problem!
∴ heat associated with metal cooling = heat associated with water warming
− (Massmetal × specific heatmetal × ∆T = massH2O × specific heatH2O × ∆T
− (48.9 g × Cs × (28.37 - 95.72) = 43.58 g × 4.184 J/g⋅ºC × (28.37 - 23.84)
3293.415 × Cs = 825.994
Cs = 0.251 J/(g deg)

Problem 3:
When ice at 0°C melts to liquid H2O, it absorbs 334 J per gram. The specific heat of water is 4.184 J g–
1 deg–1. Suppose the heat needed to melt a 35.0g ice cube is absorbed from water (0.210 kg) in a
calorimeter at 21.0°C. What is the final water temperature? [This is the kind of calculation that all
experienced party givers do before throwing a party!]
Solution: Another heat transfer problem! In this particular case, we have a glass of water at 21°C and
some ice is added, which will melt. Note that a phase transition occurs at a set temperature (i.e.,
isothermal process), so in this case the ice will melt at 0°C. However, since we have more water than
ice, once the ice has melted the ice water will warm up to its final temperature. In this case two things
are happening to the ice, while the glass of water is being cooled, i.e.,
Quantity of heat associated with (ice melting + ice water warming) = quantity of heat associated with water cooling
(massICE × heat to melt ice) + (massICE H2O × specific heat H2O × ∆T)
= –(massCal H2O × specific heat H2O × ∆T)
(35.0 g × 334 J/g) + (35.0 g × 4.184 J/g⋅deg × {Tf – 0ºC})= – (210 g × 4.184 J/g⋅deg × {Tf – 21.0ºC})
11690 + 146.44Tf = –878.64Tf + 18451.44
1025.08Tf = 6761.44
Tf = 6.6ºC
PROBLEM on page 12:
When an ideal gas expands at constant temperature (i.e., isothermal expansion), ∆U is zero.
Consider 1.00 L of an ideal gas initially at 9.00 atm and 15°C.
(a) Calculate q and w if the gas expands isothermally against a pressure of 1.00 atm.
(b) Calculate q and w if the gas expands isothermally first against a pressure of 3.00 atm,
and then against 1.00 atm.
(c) Calculate q and w if the gas expands isothermally first against a pressure of 3.00 atm,
then 2.00 atm and then against 1.00 atm.
(d) Comment on the results.

Solution:
a) V1 = 1.00 L, P1 = 9.00 atm, P2 = 1.00 atm, find V2 using P1V1 = P2V2
V2 = (9.00 atm × 1.00 L)/1.00 atm = 9.00 L
w = −P∆V = −1.00 atm (9.00 L - 1.00 L) = −8.00 atm⋅L
Conversion factor: 1 atm⋅L = 101.325 Joules
∴ w = −8.00 atm⋅L × 101.325 Joules/ atm⋅L = −811 Joules = − 0.811 kJ
∆U = q + w = 0; q = –w = +0.811 kJ

b) V1 = 1.00 L, P1 = 9.00 atm, P2 = 3.00 atm; using P1V1 = P2V2, V2 = 3.00 L

w1 = −P∆V = −3.00 atm × (3.00 L − 1.00 L) = −6.00 atm⋅L
w1 = −6.00 atm⋅L × 101.325 Joules/ atm⋅L = −0.608 kJ

V2 = 3.00 L, P2 = 3.00 atm, P3 = 1.00 atm; using P2V2 = P3V3, V3 = 9.00 L

w2 = −1.00 atm⋅L × (9.00 L - 3.00 L) = −6.00 atm⋅L
w2 = −6.00 atm⋅L × 101.325 Joules/ atm⋅L = −0.608 kJ

wTotal = w1 + w2 = −0.608 kJ + −0.608 kJ = −1.216 kJ

qTotal = –wTotal = +1.216 kJ

c) First expansion is the same as the above, i.e., V2 = 3.00 L & w1 = −0.608 kJ

V2 = 3.00 L, P2 = 3.00 atm, P3 = 2.00 atm; using P2V2 = P3V3, V3 = 4.50 L

w2 = −P∆V = −2.00 atm × (4.50 L − 3.00 L) = −3.00 atm⋅L
w2 = −3.00 atm⋅L × 101.325 Joules/ atm⋅L = −0.304 kJ

V3 = 4.50 L, P3 = 2.00 atm, P4 = 1.00 atm; using P2V2 = P3V3, V3 = 9.00 L

w2 = −1.00 atm⋅L × (9.00 L - 4.50 L) = −4.50 atm⋅L
w2 = −4.50 atm⋅L × 101.325 Joules/ atm⋅L = −0.456 kJ

wTotal = w1 + w2 + w2 = −0.608 kJ + (−0.304 kJ) + (−0.456 kJ) = −1.368 kJ

qTotal = –wTotal = +1.368 kJ

d) The conclusion is that you would get the maximum amount of work done on the surroundings
by doing the expansion in an infinite number of very small steps.
 Clicker Questions/Explanations – Thermo Part 1 – Page 13

1. Label the following process as exothermic or endothermic:

a) Your hand gets cold when you touch ice.
Subject = System = hand; Direction of heat flow: hand gets cold, so heat is lost
∴ process is exothermic
b) Water vapour condenses on a cold pipe.
Subject = System = vapour; Direction of heat flow: vapour condenses ,i.e., gas → liquid
Heat is lost from the system to slow the molecules down, ∴ process is exothermic

2. Which of the following is (are) TRUE?

a) A thermally isolated reaction vessel becomes warmer when an endothermic reaction occurs.
A vessel that is isolated from the surroundings will become cooler during an endothermic process,
as heat is transferred from the vessel to the reaction. This statement is then FALSE.
b) An exothermic reaction is characterized by a negative value of ∆H at constant P.
An exothermic reaction gives off heat, and therefore the system loses heat. The q value for the
process is then negative to represent this loss. Under constant pressure conditions q of the system
is equal to ∆H for the reaction, i.e., qSystem, P = ∆HRxn so this statement is TRUE.
c) Heat is evolved when an exothermic reaction occurs.
An exothermic reaction gives off heat, and therefore the system loses or evolves heat, which
makes this statement TRUE.

3. For the reaction: ½A2(aq) + ½B2(aq) → AB(aq); ∆H° = -265 kJ/mol, if solutions A2 and B2, starting at the
same temp., are mixed in a coffee-cup calorimeter, the reaction that occurs is
A) Exothermic and T of the resulting solution rises.
B) Endothermic and T of the resulting solution rises.
C) Exothermic and T of the resulting solution falls.
D) Endothermic and T of the resulting solution falls.
An exothermic reaction gives off heat, and this process is represented by a negative enthalpy, as the
system loses heat. In this case, the reaction takes place in water. As heat is produced, along with the
conversion of reactants to products, the surrounding water warms. When the temperature of the
solution is measured, we will observe a rise in temperature.

4. Two different metals of equal mass with different specific heat capacities absorb the same amount
of heat. Which undergoes the smallest change in temperature?
A) metal with higher specific heat capacity
B) metal with lower specific heat capacity
C) Because they have equal mass, both metals undergo the same change in temperature.
Specific heat capacity is defined as the amount of heat per unit mass required to raise the
temperature by on degree Celsius or Kelvin. If a substance has a higher specific heat capacity,
such as water, then it will absorb more heat before changing temperature than a substance with a
small value, such a metal..
5. A 50.0 g sample of water at 80°C is added to a 100.0 g sample of water at 20°C. The final
temperature of the water should be
A) between 20°C & 50°C. B) 50°C. C) between 50°C & 80°C.

As we are mixing water with water, the specific heat capacity value is the same.
If we were mixing equal amounts of water, the final temperature would end up midway between
20°C and 80°C, that is 50°C, since the heat capacity of the two samples would be the same, i.e.,
mass × specific heat capacity = heat capacity. However, since the amount of water is different, the
heat capacity will also be different and the larger sample will shift the final temperature closer to
it. Since we have more cooler water, the final temperature will then end up between 20°C and
50°C. To determine the actual final temperature, we would need to carry out the following
calculation:
Amount of heat to cool 50 g water = Amount of heat to warm 100 g water
– q (50.0 g H2O @ 80°C ) = +q (100.0 g H2O @ 20°C)
–{50.0 g × 4.184 J g-1 deg-1 × (Tf – 80) deg} = 100.0 g × 4.184 J g-1 deg-1 × (Tf – 20) deg
–209.2Tf + 16736 = 418.4Tf – 8368
25104 = 627.6Tf
Tf = 40°C

6. Calculate the work needed to make room for products in the combustion of 1 mole of C3H8(g) to CO2
and water vapour where reactants and products are brought to STP.
A) +2.48 kJ B) +2.27 kJ C) –2.27 kJ D) –2.48 kJ E) no work is required
Rxn: C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(g) @ STP
Standard temperature & pressure (STP) = 273.15 K (0 °C) and
an absolute pressure of exactly 100 000 Pa (1 bar, 14.7 psi, 0.98692 atm).
w = – Pext.∆V ≅ –∆ngasRT (Assuming ideal gas behaviour.)
∆ngas = Products – Reactants = (3+4) – (1+5) = 1 mol
w = –∆ngasRT = – (1 mol)(8.314 J·mol-1·K-1)(273 K) × 1 kJ/1000 J= –2.27 kJ

7. Calculate the change in internal energy for a system that does 500 kJ of work on the surroundings
when 300 kJ of heat are absorbed by the system.
A) – 800 kJ B) – 200 kJ C) 0 kJ D) +50 kJ E) +75 kJ

To solve for the change in internal energy use: ∆U = q + w

Now use the direction of energy flow given to assign signs to both the values for work and heat, i.e.,
work is done on the surroundings, ∴w = – 500 kJ.
heat is absorbed by the system, ∴q = +300 kJ
∴∆U = 300 kJ – 500 kJ = –200 kJ
 Thermo - Part II

Page 21
Question: Calculate the heat required to decompose limestone: CaCO3(s) → CaO(s) + CO2(g)
You are given: ∆H°f [CaCO3(s)] = –1206.9 kJ/mol
∆H°f [CaO(s)] = –635.1 kJ/mol
∆H°f [CO2(g)] = –393.5 kJ/mol

1) The Long Way (Hess's Law):

(1) Ca(s) + C(s) + 3/2O2(g) → CaCO3(s); ∆H°f = –1206.9 kJ/mol
(2) Ca(s) + ½O2(g) → CaO(s); ∆H°f = –635.1 kJ/mol
(3) C(s) + O2(g) → CO2(g); ∆H°f = –393.5 kJ/mol
Want: CaCO3(s) → CaO(s) + CO2(g)
Therefore, flip equation (1) and add (2) and (3):
CaCO3(s) → Ca(s) + C(s) + 3/2O2(g) ; ∆H°f = +1206.9 kJ/mol
Ca(s) + ½O2(g) → CaO (s); ∆H°f = –635.1 kJ/mol
C(s) + O2(g) → CO2(g); ∆H°f = –393.5 kJ/mol
CaCO3(s) → CaO(s) + CO2(g) ; ∆H°Rxn = +178.3 kJ/mol

2) The Short Way:

∆H°rxn = Σn∆Hf°(products) – Σn∆Hf°(reactants)
∆H°rxn = ∆H°f [CaO(s)] + ∆H°f [CO2(g)] – ∆H°f [CaCO3(s)]
∆H°rxn = (–635.1 kJ/mol) + (–393.5 kJ/mol) – (–1206.9 kJ/mol)
∆H°rxn = +178.3 kJ/mol

Page 22
Problem 1:
Calculate ∆H°Rxn for the reaction: CH4(g) + 2O2(g) → CO2(g) + 2H2O(l)
∆H°rxn = Σn∆Hf°(products) – Σn∆Hf°(reactants)
∆H°rxn = ∆H°f [CO2(g)] + 2∆H°f [H2O(l)] – ∆H°f [CH4(g)] – 2∆H°f [O2(g)]
∆H°rxn = (–393.5 kJ/mol) + 2(–285.8 kJ/mol) – (–74.87 kJ/mol) – 2(0 kJ/mol)
∆H°Rxn = –890 kJ/mol
Problem 2:
Given
(a) 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(l); ∆H = –1169 kJ/mol
(b) 4NH3(g) + 3O2(g) → 2N2(g) + 6H2O(l); ∆H = –1530 kJ/mol
What is ∆H°f for NO(g)?
Want: ½N2(g) + ½O2(g) → NO(g); ∆H°f[NO(g)]
Add (a) to the reverse of (b):
2
(a) 4NH3(g) + 5O2(g) → 4NO(g) + 6H2O(l); ∆H = –1169 kJ/mol
(-b) 2N2(g) + 6H2O(l) → 4NH3(g) + 3O2(g) ; ∆H = +1530 kJ/mol
2N2(g) + 2O2(g) → 4NO(g) ∆HRxn = +361 kJ/mol
Divide by 4: ½N2(g) + ½O2(g) → NO(g) ∆H°f = +361/4 = 90.2 kJ/mol
Problem 3:
Given ∆H°f [C2H6(g)] = –85 kJ/mol; ∆H°f [H2O(l)] = –286 kJ/mol; ∆H°f [CO2 (g)] = –394 kJ/mol
Calculate how much energy is released when 1.00 g C2H6 (g) is burned in air at 25°C and 1.01 × 105 Pa.

Reaction: C2H6(g) + 7/2 O2(g) → 2CO2(g) + 3H2O(l)

∆H°reaction = Σn∆H°f (products) – Σn∆H°f (reactants)

∆H°rxn = 2 × ∆H°f [CO2(g)] + 3 × ∆H°f [H2O(l)] – ∆H°f [C2H6 (g)] – (7/2) × ∆H°f [O2(g)]
∆H°Rxn = 2(-394) + 3(-286) – (-85) – 7/2(0) = -1561 kJ/mol
1.00 g C2H6 = 0.0332 mol C2H6
∴-1561 kJ/mol × 0.0332 mol C2H6 = - 51.9 kJ.
1.00 g C2H6 evolves 51.9 kJ of energy upon combustion.

Example from Nature :

The Bombardier Beetle defends itself by "shooting" a hot solution of benzoquinone at its enemies.
Reaction: C6H4(OH)2(aq) + H2O2(aq) → C6H4O2(aq) + 2H2O(l)

(a) Calculate ∆H°Rxn for this reaction given:

(i) C6H4(OH)2(aq) → C6H4O2(aq) + H2(g); ∆H°Rxn = +177 kJ/mol
(ii) ½O2(g) + H2O(l) → H2O2(aq); ∆H°Rxn = + 94 kJ/mol
(iii) H2(g) + ½O2(g) → H2O(l); ∆H°f = –286 kJ/mol

Solution: Add (i) to (iii) and the reverse of (ii):

(i) C6H4(OH)2(aq) → C6H4O2(aq) + H2(g); ∆H°Rxn = +177 kJ/mol

(iii) H2(g) + ½O2(g) → H2O(l); ∆H°f = –286 kJ/mol
(-ii) H2O2(aq) → ½O2(g) + H2O(l) ; ∆H°Rxn = –94 kJ/mol

C6H4(OH)2(aq) + H2O2(aq) → C6H4O2(aq) + 2H2O(l) ; ∆H°Rxn = –203 kJ/mol

(b) Calculate the rise in temperature of 4.0 mg H2O produced by oxidation of 8.0 × 10–6 mol C6H4(OH)2.
Solution:
203 kJ is released per 1 mol of C6H4(OH)2(aq), therefore
8.0 × 10–6 mol × 203 kJ/mol = 1.6 × 10–3 kJ = 1.63 Joules of energy released
q = m × Cs × ∆T = (4.0 mg × 1 g/1000 mg) × 4.184 J/g⋅°C × ∆T = 1.63 Joules
0.0167 ∆T = 1.63 Joules
∆T = 97C° ---> hot stuff!
 Thermo - Part III

Page 28
Problems:
1. Given the following, determine a value for the N–N bond enthalpy in hydrazine, N2H4(g) (a rocket fuel
which is discussed on p. 251 (p. 253) in the text).
Heat of formation of liquid hydrazine is +51 kJ mol– 1
Heat of vaporisation of liquid hydrazine is +48 kJ mol–1
Bond Energies: N≡N is +942 kJ H–H is +432 kJ N–H is +386 kJ

Solution: N2(g) + 2H2(g) → N2H4(l); ∆H°f = +51 kJ/mol

N2H4(l) → N2H4(g); ∆H°vap = +48 kJ/mol
N2(g) + 2H2(g) → N2H4(g); ∆H°Rxn = +99 kJ/mol

Now that all of the above is in the gas phase, we can use bond energies:
∆H°Rxn = +99 kJ/mol = BE(N≡Ν) + 2BE(H–H) – BE(N–N) – 4BE(N–H)
+99 kJ/mol = 942 kJ/mol + 2(432 kJ/mol) – BE(N–N) – 4(386 kJ/mol)
+99 kJ/mol = 262 kJ/mol – BE(N–N)
∴BE(N–N) = 163 kJ/mol

2. Given the following (kJ) data, estimate a value for the CS bond enthalpy in CS2(g). [CS2 is isostructural with CO2].
∆H(combustion) CS2(l) –1108, C(s) –393, S(s) –297;
∆H(atomisation) C(s) +711, S(s) +280 kJ
∆H(vaporisation) CS2(l) +27 kJ

Solution: First write out the thermochemical equations to draw connections:

(1) CS2(l) + 3O2(g) → CO2(g) + 2SO2(g); ∆H°comb = –1108 kJ/mol
(2) C(s) + O2(g) → CO2(g) ; ∆H°comb = –393 kJ/mol
(3) S(s) + O2(g) → SO2(g); ∆H°comb = –297 kJ/mol
(4) C(s) → C(g) ; ∆H°atom = +711 kJ/mol
(5) S(s) → S(g); ∆H°atom = +280 kJ/mol
(6) CS2(l) → CS2(g) ; ∆H°vap = +27 kJ/mol
To find the CS bond enthalpy, want the following equation: CS2(g) → C(g) + 2S(g)
Therefore, manipulate the above equations to arrive at this overall equation:
i.e., Flip (6), add (1), (4), twice (5) to the reverse of (2) & twice the reverse of (3).
(-6) CS2(g) → CS2(l); –∆H°comb = –27 kJ/mol
(1) CS2(l) + 3O2(g) → CO2(g) + 2SO2(g); ∆H°comb = –1108 kJ/mol
(-2) CO2(g) → C(s) + O2(g); –∆H°comb = +393 kJ/mol
(-3) 2SO2(g) → 2S(s) + 2O2(g); –2×∆H°comb = (–2 × –297) = +594 kJ/mol
(4) C(s) → C(g); ∆H°atom = +711 kJ/mol
(5) 2S(s) → 2S(g); 2×∆H° atom = (2 × 280) = +560 kJ/mol
CS2(g) → C(g) + 2S(g); ∆H°Rxn = +1123 kJ/mol
S=C=S 0 0 BE(C=S) = +1123/2 = 562 kJ/mol
Question: Which of the following ionic compounds has the largest lattice energy? (p. 30)
A) CsI charges: Cs+ & I– radii: very large cation & anion, so separation b/w ions will be very large
+ –
B) NaCl charges: Na & Cl radii: medium cation + large anion making = relatively large separation
+ –
C) LiF charges: Li & F radii: small cation & anion = small separation
+ –
D) CsF charges: Cs & F radii: very large cation + small anion = medium to large separation
2+ 2–
E) MgO charges: Mg & O radii: small cation & anion = small separation – combo makes largest value

PROBLEMS (p. 31):

2. Calculate the lattice enthalpy of calcium sulphide from the following information:
enthalpy of formation for Ca(g): + 178 kJ/mol Ca(s) → Ca(g); ∆H°f = +178 kJ/mol
1st ionization energy for Ca(g): + 590 kJ/mol Ca(g) → Ca+(g) + e–; ∆H°IE(1) = +590 kJ/mol
nd + 2+
2 ionization energy for Ca(g): +1145 kJ/mol Ca (g) → Ca (g) + e ; ∆H°IE(2) = +1145 kJ/mol
–

enthalpy of formation for S(g): + 279 kJ/mol S(s) → S(g); ∆H°f = +279 kJ/mol
electron-gain enthalpy for S(g): – 200 kJ/mol S(g) + e –
→ S –
(g); ∆H°EG = – 200 kJ/mol
electron-gain enthalpy for S–(g): + 532 kJ/mol S–(g) + e– → S2–(g); ∆H°EG = +532 kJ/mol
enthalpy of formation for CaS(s): – 482 kJ/mol Ca(s) + S(s) → CaS(s); ∆H°f = –482 kJ/mol

Want: CaS(s) → Ca2+(g) + S–(g)

Hess’ Law manipulations:

CaS(s) → Ca(s) + S(s); –∆H°f = +482 kJ/mol
+ Ca(s) → Ca(g); ∆H°f = +178 kJ/mol
+ Ca(g) → Ca+(g) + e–; ∆H°IE(1) = +590 kJ/mol
+ Ca+ (g) → Ca2+(g) + e–; ∆H°IE(2) = +1145 kJ/mol
+ S(s) → S(g); ∆H°f = +279 kJ/mol
+ S(g) + e –
→ S –
(g); ∆H°f = – 200 kJ/mol
+ S –
(g) + e –
→ S 2–
(g); ∆H°f = +532 kJ/mol
CaS(s) → Ca2+(g) + S–(g) ; ∆H°Lattice = +3006 kJ/mol

3. Calculate the lattice enthalpy of calcium bromide. Here is some information to help you complete this
calculation:
enthalpy of formation of CaBr2: – 683 kJ/mole Ca(s) + Br2(l) → CaBr2(s); ∆H°f = –683 kJ/mol
bond enthalpy of Br2(g): + 112 kJ/mole Br2(g) → 2Br(g); ∆H°BE = +112 kJ/mol
electron-gain enthalpy for Br(g): – 325 kJ/mol Br(g) + e– → Br–(g); ∆H°EG = –325 kJ/mol

Want: CaBr2(s) → Ca2+(g) + 2Br–(g) ; ∆H°Lattice = ?

Solution:
CaBr2(s) → Ca(s) + Br2(l) ; –∆H°f = +683 kJ/mol
+ Ca(s) → Ca(g); ∆H°f = +178 kJ/mol
+
+ Ca(g) → Ca (g) + e ;–
∆H°IE(1) = +590 kJ/mol
+ 2+
+ Ca (g) → Ca (g) + e ; –
∆H°IE(2) = +1145 kJ/mol
+ Br2(l) → Br2(g); ∆H°vap = +30.91 kJ/mol
+ Br2(g) → 2Br(g); ∆H°BE = +112 kJ/mol
+ 2Br(g) + 2e → 2Br (g);
– –
2×∆H°EG = (2×–325) = –650 kJ/mol
CaBr2(s) → Ca2+(g) + 2Br–(g) ; ∆H°Lattice = +2089 kJ/mol

QUESTIONS: Which substance in each pair has the higher molar entropy? (p. 35)
1. A) CH4(g) < B) C3H8(g) (more atoms = higher entropy)

2. A) KCl(aq) > B) KCl(s) (mixing KF and water would produce more entropy than just a solid)

3. A) O2(g, 2 atm, 300 K) < B) O2(g, 1 atm, 300 K) (higher P reduces V and reduces entropy)

4. A) N2(g, 1 atm, 273 K) < B) N2(g, 1 atm, 450 K) (higher T increases energy and entropy)

Examples: Predict the SIGN of ∆S

1. 2H2(g) + O2(g) → 2H2O(l) (3 moles of gas to 2 moles of liquid results in a negative change in entropy)

2. 3H2(g) + N2(g) → 2NH3(g) (4 moles of gas to 2 moles of gas results in a negative change in entropy)

3. H2O(l) → H2O(g) (1 mole of liquid to 1 mole of gas results in a positive change)

4. CaCO3(s) → CaO(s) + CO2(g) (1 mole of solid to 1 mole of solid and 1 mole of gas = positive change)

5. O2(g) → O2(aq) (1 mole of gas to 1 mol of aqeous solution = negative change)

Problems (p. 36):

1. Hydrazine and hydrogen peroxide are used as rocket fuel. Using tabulated data, calculate ∆S° for the reaction:
N2H4(l) + 2H2O2(l) → N2(g) + 4H2O(g), ∆H° = –642 kJ mol–1
∆S°Rxn = 191.6 + 4(188.72) – 121.21 - 2(109.62) = +606.0 J K–1 mol–1

2. (a) H2O(l) → H2O(g); S°Rxn = 188.72 – 69.91 = 118.81 J K–1

(b) CH4(g) + 2O2(g) → CO2(g) + 2H2O(l); ∆S°Rxn = 213.68 + 2(69.91) – 186.27 – 2(205.03) = –242.83 J·K–1

EXAMPLE TO CONTEMPLATE:
2H2O(g) → 2H2(g) + O2(g)
∆S°Rxn = 2(130.59) + (205.03) – 2(188.72) = +88.77 J/K

∆Η°Rxn = 2∆H°f (H2O, g) – [2∆H°f (H2, g) + ∆H°f (Ο2, g)] = 2(−241.8) – 2(0) + 0 = – 483.6 kJ/mol
 Clicker Questions
Qu#1: Which of the following rxns has ∆H°Rxn equal to the bond enthalpy of the bond that is broken?
A. HCl (g) → H +(aq) + Cl –(aq)
B. HCl (g) → H +(g) + Cl –(g) BE = energy required to break a mole of
C. HCl (g) → H (g) + Cl (g) covalent bonds in the gas phase

Qu#2: Given the following average bond energies: 432 (H–H); 154 (F–F); 565 (H–F) kJ/mol
Estimate ∆H for: H2(g) + F2(g) → 2HF(g).
A) −21 kJ
B) +21 kJ ∆HRxn = (H-H) + (F-F) – 2(HF) = 432 + 154 – 2(565) = –544 kJ
C) +544 kJ Section 9.11 Bond Energy
D) –544 kJ
E) +1151 kJ
Qu#3: Which molecule has the lowest nitrogen-nitrogen bond energy?
A) N2H4 H2N–NH2 (N–N: 159 kJ/mol) Section 9.11 Bond Energy
B) N2F2 F–N=N–F (N=N: 418 kJ/mol)
C) N2 N≡N (N≡N: 950 kJ/mol)
D) All of the bonds have the same bond energy since they all involve two nitrogens.

Qu#4: Consider the reaction: 2HCl(g) + 185 kJ → H2(g) + Cl2(g) Which of the following is true?
A) The chemical bonds in the products are weaker than those in the reactants.
2(H-Cl) – H-H – Cl-Cl = + 185; ∴2(H-Cl) > H-H + Cl-Cl True
B) If thermally isolated, the reaction mixture will get cooler as the reaction proceeds.
Heat is needed to drive reaction, so heat would be drawn from rxn mixture - True
C) The HCl(g) has a negative heat of formation. elements → HCl(g); reverse and ½ rxn – True
D) The reaction is endothermic. True - heat is added
E) All of these are true.

Qu#5: Which of the following processes would be expected to have the SMALLEST increase in
∆S°rxn per mole of benzene?
A) C6H6(s) → C6H6(l) solid → liquid (A smaller difference in S values)
B) C6H6(s) → C6H6(g) solid → gas (large difference)
C) C6H6(l) + Br2(l) → C6H5Br(l) + HBr(g) liquids → liquid + gas (medium difference)
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D) C6H6(l) + O2(g) → 6CO(g) + 3H2O(g) liquid + gas → 9 moles of gas (v. large difference)
2
15
E) C6H6(l) + O2(g) → 6CO2(g) + 3H2O(g) liquid + gas → 9 moles of gas (v. large difference)
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 THERMO - PART 4 - SOLUTIONS

Page 44-45
Example of calculating ∆G°Rxn from ∆H°Rxn and ∆S°Rxn values
Equation: C(s) + 2H2(g) → CH4(g) Note: This is a formation equation for CH4(g)
∆H°Rxn = (-74.87) – 0 – 2() = –74.87 kJ/mol = ∆H°f(CH4, g)
∆S°Rxn = (186.1) – (5.740) – 2(130.6) = –80.84 J·mol-1·K-1
∆G°Rxn = ∆H°Rxn - T ∆S°Rxn OR ∆G°Rxn @ 25°C= Σn∆G°m,f (Prod’ts) – Σn∆G°m,f (React’ts)
∆G°Rxn @ 298 K = (-74.87 kJ/mol) – 298K(–80.84 J·mol-1·K-1 × 1 kJ/1000 J) = –50.79 kJ/mol
OR ∆G°Rxn @ 298K = (–50.80) – 0 – 2(0) = –50.80 kJ/mol
Note ∆G°Rxn = ∆G°f (CH4, g) = –50.8 kJ/mol ∴ Rxn favours products at 298 K (i.e., K is large)
Note: At 1000K, can only use the ∆H°Rxn - T ∆S°Rxn relationship, i.e.,
∆G°Rxn @ 1000 K= –74.8 kJ – {1000 K × –80.8 J/K × 1 kJ/ 1000 J} = + 6 kJ
Reaction is entropically unfavoured at high T.

Page 45: Review Question

∆GRxn Reaction? ( , → or ←)
negative Reactants → Products
zero Reactants Products
positive Reactants ← Products
Page 47: Example: N2(g) + 3H2(g) 2NH3(g) At 298K,the partial pressures in a rxn mixture
are PN2 = 0.25 atm, PH2 = 0.55 atm and PNH3 = 0.95 atm. Determine ∆Grxn.
Step 1: ∆G°Rxn = Σn∆G°f (Prods) - Σn∆G°f (Reacts) = 2(-16.40) – 0 – 3(0) = –33.28 kJ/mol
Step 2: Q = [Prod]/[Reactants] = (0.95)2/{(0.25) × (0.55)3} = 21.7
Step 3: ∆Grxn = ∆G°rxn + RT ln Q = –33.28 kJ/mol + (8.314×10-3 kJ·mol-1·K-1 )(298 K) ln (21.7)
∆Grxn = -25.66 kJ
∆Grxn is negative. Therefore, the rxn is moving in the forward direction (and making more products

Page 50: Problem 2: NH3(g) + H2O(l) NH4+(aq) + OH–(aq); K = 1.75 × 10-5 at 25°C.
a) ∆G°rxn = – RT ln K = - (8.314)(298 K) ln 1.75 × 10-5 = 27138 J/mol = 27.138 kJ/mol
b) Q = {[NH4+]×[OH–]}/[NH3] = (1.0×10-6 )2/(0.050) = 2.0×10-11
∆Grxn = RT ln (Q/K) = ∆G°rxn + RT ln Q
∴ ∆Grxn = (8.314)(298 K) ln (2.0×10-11/1.75 × 10-5) = -33898 J/mol = -33.90 kJ/mol
OR ∆Grxn = 27.138 kJ/mol + (8.314×10-3 kJ·mol-1·K-1)(298 K) ln (2.0×10-11) = -33.90 kJ/mol

Note: Since Q < K, the reaction will move in the direction to make more products.
Since ∆Grxn is negative, the reaction will move in the direction to make more products.

1
Clicker Question#1: For which of the following reactions is ∆G ° negative?
A) HCl(aq) → H+(aq) + Cl−(aq) (Strong acid dissociates – ions are favoured as K is large;∆G ° < 0)
+ −
B) AgCl(s) Ag (aq) + Cl (aq) (AgCl is an insoluble salt; salt is favoured as Ksp is small;∆G ° > 0)
C) HCO3−(aq) CO32–(aq) + H+(aq) (Bicarbonate is a weak base; Kb is small; products not favoured ;∆G ° < 0)
D) All.
E) None.

Clicker Question#2: A liquid is vapourised at its normal boiling point at constant P.

What is true about ∆G ?
A) The value is negative. Rxn: liquid gas @ Tboiling; K = Pgas = atmospheric pressure
B) The value is positive. KEY: Reaction is at equilibrium and Q = K
C) The value is zero. ∴∆ G = RT ln (Q/K) = 0

Clicker Question#3: A liquid is vapourised at its normal boiling point at constant P.

What is true about ∆G °?
A) The value is negative. Key: “normal boiling point”; Normal bpt is reached when
B) The value is positive. vapour pressure of liquid = 1 atm; ∴K = 1
C) The value is zero. ∆G°= -RT ln K = = -RT ln(1) = 0

Page 52: Problem 1: For the reaction (at 25°C), 2H2O(l) H3O+(aq) + OH–(aq), KW = 1.00 × 10-14
and ∆H° = +55.8 kJ/mol, calculate the pH of boiling water.
METHOD 1:
a) ∆G°@ 298K = –RT ln K = –(8.314×10-3 kJ·mol-1·K-1)(298 K) ln (1.00 × 10-14) = 79.867 kJ/mol
b) ∆S° = (∆G° − ∆H°)/−Τ = (79.867 - 55.8)/-298 K = -0.0808 kJ·mol-1·K-1 = −80.8 J·mol-1·K-1
c) ∆G°@ 373K = (55.8) − (373 Κ)(−0.0808 kJ·mol-1·K-1) = 85.9 kJ/mol
d) K = e– ∆G°/RT = exp{-85.9 kJ/mol/[(8.314×10-3 kJ·mol-1·K-1)(373 K)]} = e-27.71 = 9.3×10-13
e) [H3O+] = √Kw = √9.3×10-13 = 9.6×10-7 and pH = - log (9.6×10-7 ) = 6.0

OR
METHOD 2:
a) ln(K2/K1) = (∆H°/R) [(T2 – T1)/T1T2]
ln(K2/1.00 × 10-14) = (55800/8.314)×[(373 – 298)/(298×373)]
K2 = Kw @ 100°C = 9.3 × 10–13
+ -13
b) [H3O ] = √Kw = √9.3×10 = 9.6×10-7 and pH = - log (9.6×10-7 ) = 6.0

Page 53: Problem 2: At 25°C & 1 atm, ∆H°f (I2, g) = +62.4 kJ/mol & ∆G°f (I2, g) = +19.4 kJ/mol.
(i) The formation of I2(g) : I2(s) I2(g) , i.e., elements form one mole of something
(ii) ∆G° = ∆H° – T∆S°; ∴∆S° = (∆G° − ∆H°)/−Τ = (19400 – 62400 J/mol)/−298 = 144 J·mol-1·K-1

2
 (iii) Since both ∆H° and ∆S° are positive, we would need a high enough T to make the
products favoured. To find the transition T, set ∆G° = 0 and solve for T, i.e.,
0 = ∆G° = ∆H° – T∆S°; T = ∆H°/∆S° = 433K = 160°C
So, at T > 160°C, ∆G° will be a negative number, and the products will be favoured.
(iv) ∆G° = – RT ln K; K = exp {–∆G°/RT}
K = exp {–(19.4 kJ/mol)/[(8.314×10-3 kJ·mol-1·K-1)(298 K)]} = 3.98×10–4
K = P(I2, g) = 3.98×10–4, i.e., the vapour pressure of I2(s) = 3.98×10–4 atm
This is a small but appreciable amount, enough that your nose can detect it!

Page 53: Problem 3: Pressure of I2(g) = 1.0 × 10–6 atm, calculate ∆G for the process. Hint: Q = ?
Note: “Vapour pressure”at a specific T refers to the system being at equilibrium
and “pressure of I2(g)” refers to some other point, i.e., Q.
We know that ∆G = RT ln (Q/K). Based on the previous problem, we determined K = 3.98×10–4 at
25°C. This question indicates that Q = 1.0 × 10–6 (seeing the pressure of I2(g) = Q), and so we can
just solve for ∆G using the above relationship at 25°C, i.e.,
∆G = (8.314 × 10–3 kJ/mol K) (298 K) ln (1.0 × 10–6 /3.98×10–4)
∆G = –14.8 kJ/mol
i.e., the rxn to produce I2(g) is spontaneous At this point, the reaction is not at equilibrium and
will proceed from left to right (to form more products).

Page 53: Extra Question: At what temperature will the vapor pressure of water equal 600 Torr?
Assume enthalpy and entropy changes to be independent of temperature.
Rxn: H2O(l) H2O(g); K = P(H2O, g)
Vapour Pressure of water = 600 Torr MUST convert to atm!! (Use: 1 atm = 760 Torr)
Vapour Pressure of water = 600 Torr × 1 atm/760 Torr = 0.789 atm
∴ Keq = 0.789

∆G° = –RT lnKeq & ∆G° = ∆H° – T∆S°

We have K and can calculate ∆H° and ∆S° to solve for the missing T, i.e.,
∴– RT lnKeq = ∆H° – T∆S°
Use Appendix C to find values to solve for:
∆H°(298K) = -241.8 – (-285.8) = +44.01 kJ mol–1
∆S°(298K) = 188.7 – 69.95 = 118.78 J K–1 mol–1
Using: – RT lnKeq = ∆H° – T∆S°
–8.314 J K mol T ln(0.789) = 44.01 × 103 J/mol – (118.78 J K–1 mol–1)T
–1 –1

1.97T = 44010 – 118.78T

T = 364 K = 91ºC
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ANSWERS to Questions at the end of Thermo – Part 5:
1. ∆G°298 = ∆G°f (H2O, g) – ∆G°f (H2O, l)
Get values from Appendix C:
∆G°298 = –228.59 – (–237.18) = +8.60 kJ mol–1
Since ∆G°298 is positive the reaction H2O(l) H2O(g) does NOT favour the formation of the product
(i.e., water vapour) at 25°C, but the reverse reaction would. Note that just because a reaction does not
favour the products, products are still formed to some extent.

2. We want to find Kp = P(H2O, g) = Keq; Recall that Keq = e–∆G°/RT

From the previous calculation, ∆G° for the evaporation of water = +8.60 kJ mol–1 @ 298 K
KP = e–∆G°/RT
= exp[ (–8.60 kJ/mol × 1000J/kJ)/(8.314 J/mol K× 298 K) ]
= exp[–3.47]
= 3.11 × 10–2 (Note: There are no units for K!)
∴ Vapour Pressure = 3.11 × 10–2 atm at 298 K (Note: Vapour Pressure HAS units!)
You should be able to show for yourselves that if the vapour pressure of water in the atmosphere is
less than this value at 298 K, then water (e.g., puddles) WILL spontaneously evaporate at 298 K (i.e.,
Q < K). By similar calculations you can show that ICE or SNOW will vanish (i.e., sublime) away on
a very cold day during which there is abundant sunshine and a very low relative humidity.

3. Vapour Pressure = 1 atm , therefore Keq = 1 & ∆G° = –RTlnKeq = –RTln(1) = 0

If ∆G° = ∆H° – T∆S° = 0, then T = ∆H°/∆S° = ∆H°vap/∆S°vap = Tb
∆H°(298) = ∆H°f (H2O(g)) – ∆H°f (H2O(l))
= –241.83 – (–285.4)
= +44.01 kJ mol–1

∆S°(298) = S°m (H2O(g)) – S°m (H2O(l))

= 188.72 – 69.94
= 118.78 J K–1 mol–1
Tb = ∆H°vap/∆S°vap
= 44.01 × 1000 J mol–1/118.78 J K–1 mol–1
= 371 K
{correct value 373 K – but we made the assumption that ∆H° and ∆S° were independent of T.}
The "normal boiling point" is the temperature at which
the vapour pressure of a liquid is equal to 1 atm.

4. Eq’n: AgCl(s) Ag+(aq) + Cl–(aq); Ksp = [Ag+][Cl–] = s2 (Note: Ksp is discussed in Sect. 17.1)
Need K, why, how?
Get ∆G°, how?
∆G°f values from tables and calculate "Products minus Reactants".
∆G° = +55.6 kJ
K = e-∆G°/RT = 1.8 × 10–10 and solubility (s) = √ Ksp = 1.3 × 10–5 M.

1
5. Use the van’t Hoff equation: ln(K2/K1) = (∆H°/R)[(T2 – T1)/T1T2] where
K1 = 1.00×10–14 @ T1 = 298K
K2 = ? @ T2 = 373K
∆H°= 55.8 kJ/mol

K2 = 9.26×10–13 at 373K
pH = –log {K½ } = 6.02

6. A. would only be true if ∆ngas = 0 (or w = 0).

B. has an incorrect equation (correct equation: ∆U = ∆H – ∆nRT).
C. is always true IF a process is at equilibrium because when Q/K = 1, ∆G = RT ln Q/K = 0.
D. is incorrect (see B).
E. is also true.

7. ∆G° Rxn = ∆G°f (H+, aq) + ∆G°f (Ac–, aq) – ∆G°f (HAc, aq) = 0.0 + (–372.5) – (–399.6) = +27.1 kJ/mol
K = e– ∆G°/RT = e– 27200/(8.314)(298) = 1.8 × 10–5

Think about the significance of the +ve sign of ∆G°Rxn . The +ve sign tells you that UNDER
STANDARD CONDITIONS, the reaction does not favour products. However, the reverse
reaction favours the production of HAc. So HAc is more stable than Ac–(aq) and H3O+(aq).
Now we can calculate, for example, for 0.10 M acetic acid, [H3O+] = [Ac–] = 1.3×10–3 M.
Look at what happens to the value of ∆G if the concentrations of the [H3O+] and [Ac–] are
smaller than 1.3×10–3 M, say 1.0×10–5 M:
Q = {[H3O+] × [Ac–]} / [HAc] = (1.0×10–5)2/0.10 = 1.0×10–9; ln Q = -20.7
∆Grxn = ∆G°rxn + RTlnQ
= +27.1 kJ/mol + {8.314×10-3 kJ⋅mol-1⋅K-1 × 298K × (–20.7) = –24.2 kJ
So the reaction is spontaneous L → R at low [H3O+] and [Ac–] ion concentrations – and will continue
until equilibrium conditions are achieved.

8. When ∆H and ∆S are both negative, the reaction is enthalpy driven.

Using ∆G = ∆H – T∆S, we can determine the T at which the reaction changes from being
non-spontaneous (+) to spontaneous (-). That is, set ∆G = 0 and solve to T.
∴∆H/∆S = -6.90×10+3 J/-15.4 J/K = 448 K = 175°C
To make ∆G negative, T must be less than 175°C so that we minimize the impact of -T∆S.

9. A change in phase results in ∆G = 0 because the system is at equilibrium.

∆S for boiling = ∆Hvap/T = 40600J/mol/373K = 109 J/mol K.
Therefore, ∆S for condensation (the opposite of boiling) = –109 J/mol K.

10. K = 1 @ normal boiling point, so ∆G° = 0

Tboiling = ∆H/∆S = 32800 J/95.1 J/K = 345 K = 72°C

11. a) ∆G° = ∆H° – T∆S° = –33 kJ;

b) Kp = e+33000/(8.314)(298) = 6.1×105

12. ∆HoRxn = –165 kJ & ∆So Rxn = –543 J/K; ∆Go = ∆H° – T∆S° = –3.4 kJ;
K = exp{∆Go /RT} = 3.9

2
13. ∆G° = ∆H° – T∆S° = –52.9 kJ (CuSO4.5H2O is stable.);
∆G = ∆G° + RTlnQ = –17.6 kJ

14. ∆G° = –RTlnK = 80. kJ ∆S° = (∆H°–∆G°)/T = –77 J K–1

Kw at 4°C = 1.8 × 10–15 pH = 7.38 (at 4°C)

15. When no further reaction occurs, the reaction is finished, dead, i.e., at equilibrium.
∆G = ∆G° + RTlnQ = 0 & ∆G° = –RT ln K
log K = –∆G°/2.303RT & K = PHCN/{[CN–] × [H3O+]}
log K = –∆G°/2.303RT = log{(PHCN)/[CN–]} –log[H3O+]
–log[H3O+] = –∆G°/2.303RT – log{(PHCN)/[CN–]}
pH = 8.36 – (–2.40) = 10.76

16. ln(P) = 98.83/8.314 – 61320/(8.314 × 298) = 11.89 – 24.75 = –12.86 = –12.9

P = 2.6 × 10–6 atm = 0.26 Pa

17. a) ∆G = RTln (Q/K), therefore, when a reaction is at equilibrium, Q/K = 1 & ∆G = 0.

b) ∆G° = –RT ln K, therefore when a reaction at a normal boiling point, K=1 and ∆G° = 0.