CHEM 301 Unit 3 Soluion
CHEM 301 Unit 3 Soluion
1. True
2. False
Graphite is thermodynamically more stable that diamond under standard conditions.
1. Which statement would be the best interpretation of the First Law of Thermodynamics?
1. The total amount of energy in the universe is increasing.
2. The total amount of entropy in the universe is increasing.
3. The total amount of energy in the universe is constant.
4. The total amount of matter in the universe is constant.
The first law is the law of conservation of energy and mass (not matter). The second law
deals with entropy.
2. Enthalpy (H) is best defined by which of the following statements?
1. the capacity of a system to influence the entropy of its surroundings
2. pressure-volume work
3. a measure of a system's energetic degeneracy
4. none of these describe enthalpy
We know that the change in enthalpy of a sytem (whether it increases or decreases in a
given system for a given process) affects the entropy of its surroundings, thereby
influencing the spontaneity of a reaction.
3.1. Water changing from a solid to a liquid is
1. an endothermic change.
2. an exothermic change.
3. Neither an exothermic or an endothermic change
Heat is always required for melting any substance. Melting is an endothermic process.
3.2. Heat flow is considered positive when heat flows (into, out of) a system; work is
considered positive when work is done (by, on) a system.
1. out of; by
2. into; on
3. out of; on
4. into; by
Heat flow q is considered positive when heat flows into a system. Work w is considered
positive when work is done on a system.
4. Definition: state functions
An extensive state function's value is (dependent on/independent of) the amount of a given
substance. An intensive state function's value is (dependent on/independent of) the amount
of a given substance.
1. dependent on, dependent on
2. independent of, independent of
3. dependent on, independent of
4. independent of, dependent on
Extensive properties depend on the extent of the system (whence the term extensive);
intensive properties do not.
5. What is the enthalpy change for HfC(s,graphite)?
1. 1300 kJ/mol
2. 31 kJ/mol
3. 717 kJ/mol
4. 0 kJ/mol
5. 575 kJ/mol
for H2O() :
285.83 kJ/mol;
for CO2(g) :
393.51 kJ/mol;
for CaCO3(s) : 1206.9 kJ/mol;
and for HCl(aq) : 167.16 kJ/mol.
1. 72.7 kJ/mol
2. 165 kJ/mol
3. 38.2 kJ/mol
4. 98.8 kJ/mol
5. 15.2 kJ/mol
6. 116 kJ/mol
7. 215 kJ/mol
We use Hess Law:
H = Hf,prod Hf,reac = = 15.22 kJ/mol .
9. Calculation: Hesss Law and combined reaction enthalpies
Calculate the standard reaction enthalpy for the reaction:
NO2(g) NO(g) + O(g)
Using:
O2(g) 2O(g)
H = +498.4 kJ/mol
3/2 O2(g) O3(g)
H = +142.7 kJ/mol
NO(g) + O3(g) NO2(g) + O2(g)
H = -200.0 kJ/mol
1. +592 kJ/mol
2. +555 kJ/mol
3. +307 kJ/mol
4. +355 kJ/mol
5. +192 kJ/mol
Hrxn = 1/2(498.4) + -1(142.7) + -1(200.0) = +306.5
10.1. How much internal energy would be associated with the rotational motion of 1 mole of
CO2?
1. RT
2. 1/2 RT
3. 3/2 RT
4. 2 RT
Since carbon dioxide is linear, it has two rotational modes, times 1/2 RT per mode per mole
gives a total of RT.
10.2. What would be the total vibrational energy of .0833 moles of cetane (C 16H34),
assuming cetane is non-linear?
1. 72 RT
2. 144 RT
3. 12 RT
4. 6 RT
Cetane will have 150 total modes, 144 of which are vibrational, times 1/2 RT per mode per
mole times 0.0833 moles gives a total of 6 RT.
11. What energy change is associated with the reaction to obtain 1.00 mole of H2? The
balanced equation is:
2 H2O(g) 2 H2(g) + O2(g)
and the relevant bond energies are:
H-H : 436 kJ/mol; H-O : 467 kJ/mol;
O-O : 146 kJ/mol; O=O : 498 kJ/mol.
1. +425 kJ
2. +249 kJ
3. 425 kJ
4. +498 kJ
5. -498 kJ
6. 436 kJ
H = BEreac BEprod = 1868 kJ/mol 1370 kJ/mol = 498 kJ/mol
The reaction forms 2 moles of H2, so the energy to form one mole of H2 from one mole of
water vapor is half as much: 249 kJ/mol.
12.1. 1.95 mol of an ideal gas at 300 K and 3.00 atm expands from 16 L to 28 L and a final
pressure of 1.20 atm in two steps:
(1) the gas is cooled at constant volume until its pressure has fallen to 1.20 atm, and
(2) it is heated and allowed to expand against a constant pressure of 1.20 atm until its
volume reaches 28 L.
Which of the following is CORRECT?
1. w = 4.57 kJ for the overall process
2. w = 6.03 kJ for the overall process
3. w = 4.57 kJ for (1) and w = 1.46 kJ for (2)
4. w = 0 for the overall process
5. w = 0 for (1) and w = 1.46 kJ for (2)
For step (1): If there is no change in volume, w = 0.
For step (2): For expansion against a constant external pressure,
w = Pext V = (1.2 atm)(18 L 6 L) (101.325 J L1 atm1) = 1.45908 kJ .
12.2. 0.500 mole of N2(g) reacts with 1.50 moles H2(g) to produce NH3(g):
N2(g) + 3H2(g) 2NH3(g)
If this reaction is carried out in a system against a constant 0.75 atm pressure (i.e., a
piston) at 0 C, calculate the magnitude of the P V work.
3
1. 2.27 10 J
2. 22.4 J
3. 22.7 J
3
4. 22.4 10 J
3
5. 4.54 10 J
w = -nRT = -(1) (8.314) (273K) = 2269.72 J/mol
13. Which of the following are not forms of internal energy?
1. motion of molecules
2. kinetic energy
3. heat
4. potential energy
5. chemical bonds
Heat is a process function, a means by which energy is transferred between systems and
surroundings, but it is not a form of internal energy.
14. Which of the following statements concerning calorimetry is/are true?
I) Bomb calorimeters hold the volume of the system constant.
II) The calorimeter itself does not absorb heat.
III) H = q in a bomb calorimeter.
1. I, II
2. I only
3. II only
4. I, II, III
5. I, III
6. II, III
7. III only
Volume is constant in a bomb calorimeter; qv = E not H. The apparatus does absorb
heat, even though we sometimes ignore this for the sake of convenience.
15. A system did 150 kJ of work and its internal energy increased by 60 kJ. How much
energy did the system gain or lose as heat?
1. The system gained 60 kJ of energy as heat.
2. The system gained 90 kJ of energy as heat.
3. The system gained 210 kJ of energy as heat.
4. The system lost 90 kJ of energy as heat.
5. The systemlost 210 kJ of energy as heat.
E = q + w
60 = q - 150
q = 210 kJ
16.1. For the four chemical reactions
I) 3O2(g) 2O3(g)
II) 2H2O(g) 2H2(g) + O2(g)
III) H2O(g) H2O()
IV) 2H2O() + O2(g) 2H2O2()
which one(s) is/are likely to exhibit a positive S?
1. All have a positive S.
2. I, III and IV only
3. I and II only
4. III and IV only
5. II only
The Third Law of Thermodynamics states that the entropy of a perfect pure crystal at 0 K is
0. As disorder, randomness, and degrees of freedom increase, so does S. Entropy can
increase by changing phase from solid to liquid to gas, and by increasing temperature,
volume, or number of particles. In reaction I, the final state has less gas par- ticles (and
thus less entropy) than the initial state. Therefore S is negative. In reaction II, the final
state has more gas particles (and thus more entropy) than the initial state. Therefore S is
positive. III describes a phase change. Gases have more degrees of freedom, randomness,
and disorder (entropy) than liquids. The final state is a liquid and the initial state is a gas.
Therefore S is negative. In reaction IV, the final state has 0 gas particles and the initial
state has 1 mole of gas particles. Therefore S is negative.
16.2. When ngas for a reaction is large and positive S for the reaction is likely to be
(large/small) and (positive/negative).
1. large, positive
2. large, negative
3. small, positive
4. small, negative
An increase in moles of gas leads to an increase in entropy; the relative magnitudes of
ngas and S are proportional.
17. Which of the following would have the largest
absolute entropy?
1. N2(g)
2. N2(s)
3. N2(aq) (nitrogen dissolved in water)
4. N2()
S is high for systems with high degrees of freedom, disorder or randomness and low for
systems with low degrees of freedom, disorder or randomness. Gases have more degrees of
freedom, disorder and randomness than aqueous solutions, liquids, or solids.
18. Calculate the standard entropy of fusion of ethanol at its melting point 159 K. The
1
standard molar enthalpy of fusion of ethanol at its melting point is 5.02 kJ mol .
1
1
1. 5.02 kJ K
mol
1
1
2. 44.0 J K
mol
1
1
3. 31.6 J K
mol
1
1
4. +31.6 J K
mol
1
1
5. +5.02 kJ K
mol
1
Hfus = 5020 J mol
TMP = 159 K
1
1
Scond = q/T = Hfus /TMP = 5020 J mol1 K1 /159 K = +31.5723 J mol
K
19.1. Which of the following statements is FALSE?
1. The total amount of energy and matter in the Universe is constant.
2. Breaking chemical bonds is an endothermic process.
3. It is more efficient to use a primary energy source than a secondary energy source.
4. Entropy must be conserved in all chemical reactions.
The Second Law of Thermodynamics states that in spontaneous changes the universe tends
toward a state of greater disorder. Entropy is not conserved.
19.2. Which of these statements about thermodynamics is NOT TRUE?
1. The entropy of the system is always increasing.
2. Energy is conserved in chemical reactions.
3. Heat given off to the surroundings is negative in sign.
4. V , S, and H are examples of changes in thermodynamic state functions.
5. Work done on the system is positive in sign.
The entropy of a system or its surroundings may increase or decrease. The Second Law of
Thermodynamics states that in spontaneous changes, the universe tends toward a state of
greater disorder; that is, entropy increases (Suniv > 0).
20. The law states that a substance that is perfectly crystaline at 0 K has an entropy of
zero. This law is called
1. None of these
2. the first law of thermodynamics.
3. the third law of thermodynamics.
4. the second law of thermodynamics.
5. the zeroth law of thermodynamics.
The Third Law of Thermodynamics states that the entropy of a pure crystalline substance is
0 at absolute 0 K.
21. In terms of absolute entropy, which of the following is/are true?
I) W has both a real and a theoretical value.
II) The Boltzmann constant can be used when calculating S for molar quantities.
III) W for 1 mole of CO is greater than W for 1 mole of O 2.
1. III only
2. I and III
3. I, II and III
4. II only
5. I and II
6. I only
7. II and III
1.
2.
3.
4.
5.
6.
7.
-1
-0.198 kJK
-1
0 kJK
-1
0.105 kJK
-1
0.303 kJK
-1
2.40 kJK
-1
6.89 kJK
-1
-6.00 kJK
-1
-1 -1
Ssurr = -q/T = -H/T = -(393.5 kJmol )/(298 K) = -1.320 kJmol K (at constant
pressure)
-1 -1
-1 -1
-1 -1
Suniv = Ssys + Ssurr = 2.023 kJmol K - 1.320 kJmol K = 0.703 kJmol K
1 kg of dry ice = (150 g / 44.010 g/mol) = 3.408 moles
-1 -1
-1
so the total increase is (3.408 moles)*(0.703 kJmol K ) = 2.40 kJK
27. Which of the following statements is always true?
1. If the number of moles of gas does not change in a chemical reaction, then S = 0.
2. A reaction for which S, is positive is spontaneous.
3. If H and S are both positive, then G will decrease when the temperature
increases.
4. An exothermic reaction is spontaneous.
H = (+), S = (+)
G = H T S
= (+) T (+)
= (+) T
as T increases, G will decrease
28.1. What happens to CuO(s) with respect to its elements when the temperature is raised?
Sm
Hf
Gf
-1
Jmol K
Cu(s)
33.15
O2(g)
205.14
-1
kJmol
-1
kJmol
-1
CuO(s)
42.63
-157.3
-129.7
The compound is
1. more stable at higher temperatures.
2. less stable at higher temperatures.
3. Unable to determine
-1 -1
Sr = - 93.09 Jmol K
28.2. A reaction for which H is negative and S is negative
1. could become spontaneous at low temperatures.
2. is spontaneous at any temperature.
3. could become spontaneous at high temperatures.
4. is not spontaneous at any temperature.
G = H T S
To be spontaneous, G must be negative. Its a good start that H is negative, but if S is
negative, then the quantity T S is also negative, and subtracting a negative S is actually
adding it. So for G to be negative, the positive T S must be a smaller number than the
negative H. T S will be smaller at low temperatures.
29. The standard free energy of formation of CS2() is 65.3 kJmol
298 K
1. CS2() will not spontaneously form C(s) + 2 S(s).
Jmol K
-1
kJmol-1
CaC2(s)
69.96
-59.8
HCl(aq)
56.5
-167.16
CaCl2(aq)
59.8
-877.1
200.94
226.73
C2H2(g)
1. 635 K
2. 390 K
3. 573 K
4. 745 K
5. Nonspontaneous at all temperatures
6. 416 K
7. Spontaneous at all temperatures
-1 -1
Sr = 77.78 Jmol K
-1
Hr = -256.65 kJmol