signature: 192

version number
Marco Ortega garza (mao2542)

Exam 4
Dr. Cooper - Fall 2015

LOOK on the back of your bubble sheet for water data plus constants and conversion factors.

Thermodynamic Data at 25◦ C Multiple Bond Energies (kJ/mol)

∆Hf◦ S◦ C=C 602 C=N 615 C=O 799
Substance kJ/mol J/mol K C≡C 835 C=S 577 C≡O 1072
N=N 418 O=O 498 N≡N 945
CH4 (g) -75 186
C3 H8 (g) -104 270
∆U = q + w H = U + PV
C5 H12 (ℓ) -174 263
w = −P ∆V w = −∆nRT
CO (g) -111 198
∆U = ∆H − P ∆V
CO2 (g) -394 214
∆U = ∆H − ∆nRT
COCl2 (g) -220 284
∆U = qv = n Cv ∆T
Cl2 (g) — 223
∆H = qp = n Cp ∆T
H2 O (ℓ) -286 70
qsys = −qcal
H2 O (g) -242 189
qcal = qwater + qhardware
NO2 (g) 33 240
NO (g) 91 211 ∆S = qrev /T S = k ln W
N2 H4 (ℓ) 50 12
 
∆S = n Cm ln TT12
N2 O (g) 82 220  
O2 (g) — 205 ∆S = n R ln VV21

∆Hrxn =∆H1 +∆H2 +∆H3 +···

P P
Single Bond Energies (kJ/mol) ∆Hrxn
◦
= n∆Hf◦ (prod)− n∆Hf◦ (react)
H C N O S Br P P
∆Hrxn = BEreactants − BEproducts
H 436
P P
C 413 346 ∆G◦rxn = n∆G◦f (prod)− n∆G◦f (react)

N 391 305 163 ∆Srxn

◦
=
P
nS ◦ (prod)−
P
nS ◦ (react)
O 463 358 201 146
S 347 272 — — 226 G = H − TS ∆G = ∆H − T ∆S
Br 366 285 — 201 217 193 ∆Strans = ∆Htrans /Ttrans

NOTE: Please keep your Exam copy intact (all pages still stapled). You must turn in your
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 Version 192 – Exam 4 - F14 – cooper – (49220) 2
This print-out should have 25 questions.
Multiple-choice questions may continue on
the next column or page – find all choices X
before answering.

001 4.0 points

Consider the 4 chemical reactions below. T (K) Z
I. 2 H2O2 (ℓ) → 2 H2 O(ℓ) + O2 (g)
II. N2 (g) + 3 H2 (g) → 2 NH3(g)
III. CaCO3 (s) → CaO(s) + CO2 (g)
IV. SO2 (g) + H2 O(ℓ) → H2 SO3 (aq) Y
For which reaction(s) will ∆S be negative?
∆H(J)
1. I and III
Based on the plot, which answer choice
2. II and IV correct below is a correct statement regarding the
three samples of pure water?
3. II only
1. All three samples have the same heat
4. I, II and III capacity.

5. IV only 2. Sample X has the smallest mass. correct

6. III and IV 3. All three samples have different specific

heat capacities.

Explanation: 4. Sample Z has the greatest heat capacity.

The Third Law of Thermodynamics states
that the entropy of a perfect pure crystal at 5. Sample Y would require the least heat to
0 K is 0. As disorder, randomness, and de- raise its temperature by 1 K.
grees of freedom increase, so does S. Entropy
Explanation:
can increase by changing phase from solid to
It is given that the samples are all pure
liquid to gas, and by increasing temperature,
water, which ensures that all three samples
volume, or number of particles.
have the same specific heat capacity. Since the
In reaction I, the final state has more gas
samples have different changes in T for a given
particles (and thus more entropy) than the
input of energy, we can infer that all three
initial state, so ∆S is positive.
samples have different heat capacities. Since
In reaction II, the final state has fewer gas
sample X experiences the largest increase in
particles (and thus less entropy) than the ini-
T for a given amount of energy, it must be
tial state, so ∆S is negative.
the least massive sample. Sample Z would
In reaction III, the final state has more gas
actually have a heat capacity intermediate
particles (and thus more entropy) than the
between that of X and Y. Sample Y requries
initial state, so ∆S is positive.
the most heat to raise its temperature by any
In reaction IV, the final state has 0 gas
given amount.
particles and the initial state has 1 mole of
gas particles, so ∆S is negative.
003 4.0 points
Calculate the standard reaction enthalpy
002 4.0 points
for the reaction
Consider the plot below for three different
samples of pure water. C2 H5 OH(ℓ) + 3 O2 (g) → 2 CO2 (g) + 3 H2O(ℓ)
 Version 192 – Exam 4 - F14 – cooper – (49220) 3
given
C2 H5 OH(ℓ) → 2 Cgraphite (s) + 3 H2 (g) + 1/2 O2 (g) h i
∆H = 2 (91) + 2 (−286) kJ/mol
∆H ◦ = 228 kJ · mol−1 h i
CO2 (g) → Cgraphite (s) + O2 (g) − 1 (50) + 2 (0) kJ/mol
∆H ◦ = 394 kJ · mol−1 = −440 kJ/mol
H2 (g) + 1/2 O2 (g) → H2 O(ℓ)
∆H ◦ = −286 kJ · mol−1 and
h i
1. −1, 418 kJ · mol−1 correct ∆S = 2 (211) + 2 (70) J/mol · K
h i
2. −846 kJ · mol−1 − 1 (12) + 2 (205) J/mol · K
= 140 J/mol · K
3. 336 kJ · mol−1 = 0.14 kJ/mol · K
4. 730 kJ · mol−1

5. −452 kJ · mol−1 ∆G = ∆H − T ∆S
= −440 kJ/mol
Explanation:
We need to reverse and double the second − (298 K) (0.14 kJ/mol · K)
reaction as well as triple the third reaction = −482 kJ/mol
and then add all three reactions.

004 4.0 points 005 4.0 points

A system absorbs 237 J of heat while it per-
What is ∆G◦r for the combustion of liquid forms 435 J of work. What is the change in
hydrazine (N2 H4 ) to form liquid water and the internal energy of the system?
gaseous nitric oxide (NO) according to the
balanced reaction below? 1. 672 J
N2 H4 (ℓ) + 2 O2 (g) → 2 NO(g) + 2 H2 O(ℓ)
2. 198 J
1. 247 kJ/mol
3. −198 J correct
2. −482 kJ/mol correct
4. −672 J
3. −247 kJ/mol Explanation:

4. −287 kJ/mol
∆U = q + w = 237 J +− 435 J = −198 J
5. 482 kJ/mol

6. 287 kJ/mol 006 4.0 points

Explanation:
The combustion of liquid hydrazine (N2 H4 )
to form liquid water and gaseous nitric ox-
ide (NO)
occurs according to the following reaction.
N2 H4 (ℓ) + 2 O2 (g) → 2 NO(g) + 2 H2 O(ℓ)
Which of the reactions below is a formation
reaction?
1. Cdiamond (s) + 12 O2 (g) → CO(g)
2. N2 (g) + 2 H2(g) + 12 O2 (g) → N2 H4 O(g)
correct
 Version 192 – Exam 4 - F14 – cooper – (49220) 4
bomb rises from 22.65◦ C to 29.30◦ C. The heat
3. 2 Fe(s) + 3 O(g) → Fe2 O3 (s) capacity of the hardware component of the
calorimeter (everything that is not water) is
4. B2 (s) + 2 I2 (ℓ) + Cl2 (g) → 2 BI2 Cl(g) 4042 J/◦ C. What is ∆U for the combustion of
Explanation: this substance?
A formation reaction produces exactly one
mole of one product from elements in their 1. −1.48 × 103 kJ/mol correct
standard states.
2. −1.13 × 103 kJ/mol
007 4.0 points
Using bond energies, estimate the enthalpy 3. −2.48 × 104 kJ/mol
change for the reaction between hydrogen per-
oxide (H2 O2 ) and carbon disulfide (CS2 ) to 4. −1.85 × 104 kJ/mol
produce carbon dioxide (CO2 ) and hydrogen
disulfide (H2 S2 ) according to the balanced 5. −2.87 × 103 kJ/mol
equation: Explanation:
H2 O2 + CS2 → CO2 + H2 S2 mx = 2.00 g mwater = 1502 g
SH = 4.184 J/g·◦ C HC = 4042 J/◦ C
1. −292 kJ/mol correct ∆T = 29.30◦C − 22.64◦C = 6.65◦ C

2. 106 kJ/mol The increase in the water temperature is

29.30◦C − 22.65◦C = 6.65◦ C. The amount of
3. −577 kJ/mol heat responsible for this increase in tempera-
ture for 1502 g of water is
4. 577 kJ/mol  
J
q = (6.66 C) 4.184 ◦
◦
(1502 g)
5. −106 kJ/mol g· C
= 41791 J = 41.79 kJ
6. 292 kJ/mol
The amount of heat responsible for the warm-
Explanation:
ing of the calorimeter is

∆Hrxn = ΣBEbroken − ΣBEformed q = (6.65◦ C)(4042 J/◦ C)

Total bonds broken are 2 hydrogen oxygen = 26879 J = 26.88 kJ
single bonds (463 kJ/mol), 1 oxygen oxygen
single bond (146 kJ/mol) and 2 carbon sul- The amount of heat released on the reaction
fur double bonds (577 kJ/mol). Total bonds is thus 41.79 kJ + 26.88 kJ = 68.67 kJ per the
formed are 2 hydrogen sulfur single bonds given 2.00 g of substance, which converts to
(347 kJ/mol), 1 sulfur sulfur single bond (226 34.335 kJ per gram.
kJ/mol) and 2 carbon oxygen double bonds Per mol of substance, this becomes
(799 kJ/mol).  
∆Hrxn = −292 kJ/mol kJ  g 
34.335 43.0 = 1476 kJ/mol
g mol
008 4.0 points
A 2.00 gram sample of a hypothetical sub- However, since heat is released by the system,
stance with molecular weight of 43.0 g/mol the sign is negative.
undergoes complete combustion with excess
O2 in a bomb calorimeter. The tempera- 009 4.0 points
ture of the 1502 g of water surrounding the What is the value of work when an external
 Version 192 – Exam 4 - F14 – cooper – (49220) 5
pressure of 2 atm compresses a piston from an more complex than mercury. of the gases,
initial volume of 11.2 liters to a final volume methane is larger and more complex than he-
of 2 liters. lium.

1. 1.86 kJ correct 011 4.0 points

What is the total heat flow when 12 grams of
2. −18.4 kJ ice at -40◦ C are heated to become water at
25◦ C?
3. 18.4 kJ
1. 2.26 kJ
4. −1.86 kJ
Explanation: 2. 29.39 kJ
For expansion against a constant external
pressure, 3. 0.97 kJ

4. 27.12 kJ
w = −Pext ∆V
5. 4.01 kJ
= (−2 atm)(2 L − 11.2 L)
× (101.325 J · L−1 · atm−1 ) 6. 6.27 kJ correct
= 1.86 kJ .
Explanation:
H2 O(s)12 g step 1 H O(s)12◦ g −→step 2
−40◦ C −→ 2 0 C
010 4.0 points
H2 O(ℓ)12 g step 3 H O(ℓ)12◦g
Order the following from least to greatest Sm 0◦ C −→
◦: 2 25 C
H2 O2 (ℓ), Hg(ℓ), Si(s), He(g), CH4 (g) Step 1: 2.09
g·◦ C
J
· (12 g) · (0 − − 40)◦ C

= 1,003.2 J
1. H2 O2 (ℓ), Hg(ℓ), Si(s), He(g), CH4 (g) 334 J
Step 2: g · (12 g)
= 4,008 J
2. Si(s), Hg(ℓ), H2 O2 (ℓ), CH4 (g), He(g) 4.184 J
Step 3: g·◦ C · (12 g) · (25 − 0) C ◦

3. He(g), CH4 (g), H2 O2 (ℓ), Hg(ℓ), Si(s) = 1,255.2 J

Total = 1, 003.2 J + 4, 008 J + 1, 255.2 J
4. CH4 (g), He(g), Hg(ℓ), H2 O2 (ℓ), Si(s) = 6,266.4 J = 6.27 kJ

5. Si(s), Hg(ℓ), H2 O2 (ℓ), He(g), CH4 (g) 012 4.0 points

correct What, if anything, can an open system do
that a closed system cannot?
6. Si(s), H2 O2 (ℓ), Hg(ℓ), CH4 (g), He(g)
1. undergo a chemical reaction
Explanation:
Sm◦
2. exchange matter and energy
for H2 O2 (ℓ), Hg(ℓ), Si(s), He(g), CH4 (g) are
109.6, 76.0, 18.8, 126.0, and 186.3, respec- 3. nothing - they can do all the same things
tively. This problem, however, should be
approached in terms of states of matter and 4. exchange energy
molecular size and complexity. Si is the only
solid, and although larger solids can have sig- 5. exchange matter correct
nificant molar entropies, Si’s is actually quite
small. Of the liquids, hydrogen peroxide is Explanation:
 Version 192 – Exam 4 - F14 – cooper – (49220) 6
In the natural sciences an isolated system
is a physical system without any external ex- 014 4.0 points
change - neither matter nor energy (as heat A piece of a newly synthesized material of
or work) can enter or exit, but can only move mass 25.0 g at 80.0◦ C is placed in a calorime-
around inside. A closed system is capable of ter containing 100.0 g of water at 20.0◦ C. If
exchanging energy, as heat or work, but not the final temperature of the system is 24.0◦C,
capable of exchanging matter. An open sys- what is the specific heat capacity of this new
tem in contrast is capable of exchanging both material?
matter and energy. Consequently, the correct
answer is exchanging matter - a capability 1. 1.20 J/g ◦ C correct
unique to open systems.
2. 0.30 J/g ◦ C
013 4.0 points
Which of the following statements is/are true? 3. 0.84 J/g ◦ C
I) All spontaneous reactions increase the
entropy of the universe. 4. 4.76 J/g ◦ C
II) If ∆Gsys is positive for a given reaction,
then ∆Suniv must be negative. 5. 7.46 J/g ◦ C
III) Heat flow will affect the entropy of a
Explanation:
colder system more than that of a hotter
∆Tm = (24◦ C − 80◦ C) = −56◦ C
system.
∆Tw = (24◦C − 20◦ C) = 4◦ C
Cs w = 4.184 J · g−1 · ◦ C−1
1. I only
mw = 100 g mm = 25 g
Heat energy will flow out of the material
2. I, III
in to the cool water. The final temperature
of BOTH items will be 24.0◦C. We can set
3. I, II, III correct
up two expressions for heat flow using heat
capacity and set them equal and opposite to
4. III only
each other in sign:
5. I, II
−mm Cs, m ∆Tm = mw Cs, w ∆Tw
6. II only
mw Cs, w ∆Tw
Cs, m = −
7. II, III mm ∆Tm
(100 g)(4 ◦ C)
Explanation: Cs, m = −
(25 g)(−56◦ C)
Statement I is true; the second law assures
us that the entropy of the universe is always × (4.184 J · g−1 · ◦ C−1 )
increasing; all things that happen do so be- = 1.19543 J · g−1 · ◦ C−1
cause they increase the entropy of the uni-
verse.
Statement II is true; this is a mathematical 015 4.0 points
consequence of the second law equation’s re- Consider a reaction that is non-spontaneous
lationship to the Gibbs free energy equation. at high temperatures but spontaneous at low
Statement III is true; the definition of ther- temperatures. What would be the signs of
mal entropy dictates that the temperature ∆Hsys , ∆Ssys and ∆Ssurr respectively for such
of a system is inversely proportional to the a reaction?
change in entropy that results from heat flow.
∆S = q/T 1. -, +, -
 Version 192 – Exam 4 - F14 – cooper – (49220) 7
have different values.
2. -, -, - III) For a given process, ∆Usys and ∆Usurr
must have the same magnitude.
3. -, +, +
1. II, III
4. +, -, +
2. I, III
5. -, -, + correct
3. II only
Explanation:
For a reaction that is spontaneous at low 4. I only
T, but non-spontaneous at high T, ∆Hsys and
∆Ssys must both be negative. The change 5. I, II, III
from spontaneous to non-spontaneous occurs
when T becomes sufficiently large that the un- 6. I, II
favorable contribution of entropy overwhelms
the favorable contribution of enthalpy. And 7. III only correct
when ∆Hsys is negative, ∆Ssurr must be posi-
tive. Explanation:
∆H is heat transferred at constant pres-
016 4.0 points sure. For a given process ∆U and ∆H do
Calculate the entropy change for the isother- not always have different values; for example,
mal expansion of 8.80 mol of an ideal gas from they can both be zero for a given process. Be-
180 L to 324 L. cause ∆Uuniv must be zero according to the
1st law, ∆U of a system and its surround-
1. +18.6 J/K ings not only can but must have the same
magnitude and opposite signs.
2. +133 J/K
018 4.0 points
3. +58.2 J/K Based on the enthalpy of sublimation
(∆Hsub = 71.0 kJ/mol) and entropy of sub-
4. −43.0 J/K limation (∆Ssub = 243 J/mol K) of naph-
thalene, at what temperature does this phase
5. −133 J/K transition occur?

6. 0 J/K 1. 19◦ C correct

7. +43.0 J/K correct 2. 292◦ C

Explanation: 3. −272◦ C
∆S = nR ln (V2 /V1 )

324
∆S = 8.8(8.314) ln 180 4. 0◦ C
∆S = 8.8(8.314) ln (1.8)
∆S = +43.0 J/K 5. −19◦ C

017 4.0 points 6. 272◦ C

Which of the following statements is/are true?
I) For a given process, ∆H must be zero Explanation:
when external pressure is zero. ∆Hsub = 71 kJ/mol = 71000 J/mol
II) For a given process, ∆U and ∆H must Tsub = ∆H 71000
∆Ssub = 243 = 292.18 K
sub
 Version 192 – Exam 4 - F14 – cooper – (49220) 8
292.18 − 273.15 = 19.0◦ C ements.

019 4.0 points 3. Of these three species, n-hexane is most

For which phase changes described below likely to spontaneously combust.
would ∆Ssys be positive, ∆Ssurr be negative
and ∆Suniv be negative? 4. Relative to their constituent elements
benzene is less stable than propane. cor-
25◦ C rect
1. CO2 (s) −−−−−−−−→ CO2 (g)
Explanation:
−10◦ C
2. H2 O(s) −−−−−−−−→ H2 O(ℓ) correct
021 4.0 points
−10◦ C
3. H2 O(ℓ) −−−−−−−−→ H2 O(s) A block of aluminum at 25 ◦ C and 1 atm is
heated until it is a liquid at 700 ◦ C. It is then
110◦ C cooled back down until it is back in the initial
4. H2 O(g) −−−−−−−−→ H2 O(ℓ)
state of being a solid at 25 ◦ C and 1 atm. For
Explanation: this entire process (heating and cooling) ∆H
When ∆Suniv is negative, a process is non- is...
spontaneous. Based on this we can eliminate
two answer choices that describe spontaneous 1. less than ∆U
phase changes: sublimation of dry ice at 25
◦ C, freezing of water to form ice at -10 ◦ C.
2. positive
A negative ∆Ssurr results from heat flowing
from the surroundings into the system, which 3. zero correct
occurs only during melting, boiling and sub-
limation. Based on this we can eliminate 4. greater than ∆U
another answer choice that describes phase
changes in which the system releases heat to 5. negative
the surroundings: condensation of steam to
water at 110 ◦ C. By elimination, the correct Explanation:
answer must be: ice melting to form water at Since the initial and final states of the sys-
-10 ◦ C. tem are identical, and since the value of a
−10◦ C state function such as ∆H is dependent only
H2 O(s) −−−−−−−−→ H2 O(ℓ)
on the state of the system, we can conclude
that ∆H is zero.
020 4.0 points
Consider the data below regarding different
022 4.0 points
hydrocarbons.
Calculate ∆Ssurr
◦ at 25 ◦ C for the reaction
∆G◦f
chemical species kJ · mol−1 1
propane -24.29 S8 (s) + 3 F2 (g) → SF6 (g)
8
n-hexane 0.15 ∆Hr◦ = −1209 kJ · mol−1
benzene 129.85 ∆Sr◦ = −188 J · mol−1 · K−1
Which of the following statements is sup-
ported by these data? 1. −48 J · mol−1 · K−1

1. Propane cannot exist under standard con- 2. −4057 J · mol−1 · K−1

ditions.
3. 4057 J · mol−1 · K−1 correct
2. Given enough time, benzene would
form spontaneously from its constituent el- 4. 188 J · mol−1 · K−1
 Version 192 – Exam 4 - F14 – cooper – (49220) 9

5. 48 J · mol−1 · K−1

Energy −→
Explanation:
∆Hr◦ = −1209 kJ · mol−1 T = 298 K III) reactants

products
Reaction progress −→
qsurr −q −∆Hr◦ 1. I only
∆Ssurr
◦
= = =
T T 298 K
−(−1209 kJ · mol−1 ) 2. I, II and III
=
298 K
3. I and II
= 4057 J · mol−1 · K−1
4. II and III

5. II only

6. III only correct

023 4.0 points
7. I and III
Which of the following depicts a reaction
that releases energy into its surroundings? Explanation:
For a reaction to release energy into its
surroundings, the final energy of the system
must be less than the initial energy, which is
Energy −→

depicted only in item III above.

I) products
Energy −→

reactants
Reaction progress −→ reactants

products
Energy −→

Reaction progress −→
024 4.0 points
150 grams of iron is heated from 25◦ C to
II) products 150◦ C. What is ∆S for this change? The
specific heat capacity of iron is 0.450 J/g K.
reactants
1. +23.6 J/K correct
Reaction progress −→
 Version 192 – Exam 4 - F14 – cooper – (49220) 10
2. +8438 J/K

3. −8438 J/K

4. −121 J/K

5. −23.6 J/K

6. 0 J/K

7. +121 J/K
Explanation:
∆S = mC ln (T2 /T1 )
423.15


∆S = 150(0.45) ln 298.15
∆S = 150(0.45) ln (1.42)
∆S = +23.6 J/K

025 4.0 points

Consider the combustion reaction below.

2 CH3OH(g) + 3 O2 (g) → 2 CO2 (g) + 4 H2O(ℓ)

If this reaction took place in a closed,

rigid container, work would be (posi-
tive/negative/zero) and heat would be (posi-
tive/negative/zero).

1. negative, positive

2. negative, zero

3. zero, positive

4. zero, negative correct

5. positive, negative

6. positive, zero
Explanation:
Despite the fact that the reaction results in
a net decrease in moles of gas, which would
normally result in positive work (work done
on the system), the closed, rigid container pre-
cludes a change in volume and results in zero
work. Like other combustion reactions, heat
is released, and so heat would be negative.