CHEM1070A: Principles of Modern Chemistry

Tutorial for
PPT 7: Thermochemistry

Yutong Yang ( 杨雨桐 )

Email: yutong0104@gmail.com

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Q1 (5.26) For the following processes, calculate the change in internal energy of the
system and determine whether the process is endothermic or exothermic:
a) A balloon is cooled by removing 0.655 kJ of heat. It shrinks on cooling, and the
atmosphere does 382.0 J of work on the balloon.
b) A 100.0 g bar of gold is heated from 25 °C to 50 °C during which it absorbs
322.0 J of heat. Assume the volume of the gold bar remains constant.

Answers:
ΔE = Q + W
a) Q = – 0.655 kJ, W = +382.0 J
ΔE = – 0.655 kJ + 0.3820 kJ = – 0.273 kJ
Q < 0, exothermic.

b) Q = +322.0 J, W = 0
ΔE = +322.0 J
Q > 0, endothermic.

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Q2 (5.42) Without referring to any tables, predict which of the following has the
higher enthalpy in each case:
a) 1 mol CO2(s) or 1 mol CO2(g)
b) 2 mol of H atoms or 1 mol of H2(g)
c) 1 mol N2(g) at 100 °C or 1mol N2(g) at 300 °C

Answers:
a) 1 mol CO2(g)
solid → gas, sublimation is endothermic.
b) 2 mol H atoms
H2(g) → H atoms, breaking the H-H bond requires energy, endothermic.
c) 1 mol N2(g) at 300 °C
An increase in the temperature requires that heat flows into the system.

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Q3 (5.43) Consider the following reaction:
2Mg(s) + O2(g) → 2MgO(s) ΔHrxn = –1204 kJ/mol
a) Is this reaction exothermic or endothermic?
b) Calculate the amount of heat transferred when 3.55 g of Mg(s) reacts at
constant pressure. (Mg: 24.305 g/mol, O: 16.00 g/mol)
c) How many grams of MgO are produced during an enthalpy change of –234 kJ?
d) How many kJ of heat are absorbed when 40.3 g of MgO(s) is decomposed into
Mg(s) and O2(g) at constant pressure?
Answers:
a) Exothermic
b) At constant pressure:
3.55 g  1204 kJ
Q H    87.928 kJ  87.9 kJ
24.305 g/mol 2 mol
2 mol
c) mass of MgO  234 kJ  (24.305  16.00) g/mol
 1204 kJ
=15.667 g 15.7 g
d) At constant pressure:
40.3 g 1204 kJ
Q H   601.93 kJ 602 kJ
(24.305  16.00) g/mol 2 mol 4
Q4 (5.66) Given the data
N2(g) + O2(g) → 2NO(g) ΔH1 = +180.7 kJ/mol
2NO(g) + O2(g) → 2NO2(g) ΔH2 = –113.1 kJ/mol
2N2O(g) → 2N2(g) + O2(g) ΔH3 = –163.2 kJ/mol
use Hess’s law to calculate ΔH for the reaction
N2O(g) + NO2(g) → 3NO(g) ΔH = ?

Answer:
N 2 (g ) + O 2 (g )  2NO(g ) H1
1 1
NO 2 (g )  NO(g ) + O 2 (g )  H 2
2 2
1 1
N 2 O(g )  N 2 (g ) + O 2 (g ) H 3
2 2
___________________________________________________________
N2O(g) + NO2(g) → 3NO(g)
1 1
H H1  H 2   H 3
2 2
1 1
= +180.7 kJ/mol  ( 113.1 kJ/mol)  ( 163.2 kJ/mol)
2 2
= +155.65 kJ/mol = +155.7 kJ/mol 5
Q5 (5.74) Using values from the table below, calculate the value of ΔH° for the
following reaction:
4NH3(g) + O2(g) → 2N2H4(g) + 2H2O(l)

Answer:
H o  H fo,products   H fo,reactants
2 H fo [N 2 H 4 (g )]  2 H fo [H 2 O(l )]  4 H fo [NH3 (g )]  H fo [O2 (g )]
2 95.40 kJ/mol + 2 (  285.83 kJ/mol)  4 (  46.19 kJ/mol)  0
= 190.8 kJ/mol  571.66 kJ/mol  184.7 6 kJ/mol
=  196.1 kJ/mol

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Q6 (19.24) The element gallium (Ga) freezes at 29.8 °C, and its molar enthalpy of
fusion is ΔHfus = 5.59 kJ/mol.
a) When molten gallium solidifies to Ga(s) at its normal melting point, is ΔS
positive or negative?
b) Calculate the value of ΔS when 60.0 g of Ga(l) solidifies at 29.8 °C and 1 bar.
(Ga: 69.723 g/mol)
Answer:
a)
Remember that: Ssolid  Sliquid  Sgas
S is negative for solidification.
b)
60.0 g
First, calculate the moles of Ga(l ): 0.860548 mol
69.723 g/mol
Qrev
At constant T : S 
T
At constant pressure, Q H
 H fus  5.59 kJ/mol 0.860548 mol
So, S    15.9 J/K
T (29.8  273.15) K 7
Q7 (19.22) Indicate whether each statement is true or false.
a) ΔS for an isothermal process depends on both the temperature and the amount of
matter reversibly transferred.

False (depends on temperature and heat reversibly transferred)

b) ΔS is always positive for a reversible process.

False (ΔStotal = ΔSsys + ΔSsurr = 0, ΔSsys could be positive, negative, or 0.)

c) The second law of thermodynamics says that the entropy of the system decreases
for all spontaneous process.

False (the total entropy of an “isolated” system increases for spontaneous process)

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Q8 (19.41) Predict the sign of the entropy change of the system for each of the
following reactions:
a) N2(g) + 3H2(g) → 2NH3(g)
b) CaCO3(s) → CaO(s) + CO2(g)

a) ∆S < 0 (4 moles gas  2 moles gas)

b) ∆S > 0 (1 mole solid  1 mole solid + 1 mole gas)

Q9 (19.45) In each of the following pairs, which compound would you expect to
have the higher standard molar entropy:
a) C4H4(g) or C4H10(g)
b) NO2(g) or NO(g)
c) C4H10(l) or C4H10(g)
a) C4H10(g) (more atoms)
b) NO2(g) (more atoms)
c) C4H10(g) (Sgas > Sliquid > Ssolid)

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Q10. For the following reaction, at 298K and 1 bar,
CH3OH(g) → CO(g) + 2H2(g)
a) Calculate the change in standard entropy of the system ΔS°.
b) Calculate the change in standard entropy of the surroundings and the universe,
ΔS°surr and ΔS°univ.
c) Is this reaction spontaneous at 298K and 1 bar?

Answer:
a) S o  Sfo,products   Sfo,reactants
=S o  CO( g )   2 S o  H 2 ( g )   S o  CH3 OH( g ) 
197.9  2 130.58  237.6
221.46 J/(mol K)

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Q10. For the following reaction, at 298K and 1 bar, S o 221.46 J/(mol K)
CH3OH(g) → CO(g) + 2H2(g)
a) Calculate the change in standard entropy of the system ΔS°.
b) Calculate the change in standard entropy of the surroundings and the universe,
ΔS°surr and ΔS°univ.
c) Is this reaction spontaneous at 298K and 1 bar?

Answer:
b) o
H sys  H fo,products   H fo,reactants
=H of  CO( g )   2H fo  H 2 ( g )   H of  CH 3 OH( g ) 
 110.5  0  ( 201.2)
90.7 kJ/mol

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Q10. For the following reaction, at 298K and 1 bar, S o 221.46 J/(mol K)
CH3OH(g) → CO(g) + 2H2(g)
a) Calculate the change in standard entropy of the system ΔS°.
b) Calculate the change in standard entropy of the surroundings and the universe,
ΔS°surr and ΔS°univ.
c) Is this reaction spontaneous at 298K and 1 bar?
Answer:
o
b) H sys 90.7 kJ/mol
o
o
 H sys  90.7 kJ/mol
Ssurr    0.30436 kJ/(mol K)  304 J/(mol K)
T 298 K
o o o
Suniv Ssys  Ssurr 221.46  ( 304)  82.54 J/(mol K)

c) S o  0, non-spontaneous
univ

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See you next week!

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