Page 1

Chemistry 102 (Sections 4 & 5)

Drs. Composto and Pietrovito
First Exam - February 6, 2013


Name (PRINT):

TA (circle one): Martin Amy

Recitation Section (circle one): Thursday 12 - 1, 3 4, Friday 1 - 2; 2 - 3

There are 6 questions worth a total of 100 points
The exam has 10 pages, including cover, info page, & periodic table.
Show all work in space provided on the exam or on back of exam pages.
Since partial credit may be awarded, write out all steps clearly.
Units and signs must be indicated when appropriate.
Useful information is provided at the end of your exam (you may detach)
....otherwise, this is a closed book, closed notebook exam.

Please read carefully and sign the following statement:
I agree to abide by the provisions of the Code of Academic Integrity and I certify that I have
complied with the Code of Academic Integrity in taking this examination.
[NOTE - for this exam, compliance includes:
the agreement to use my calculator - ONLY as a CALCULATION aid - &
the pledge that NO other electronic or wireless devices are used in any capacity.]


Signature:

Please do not write below this line

1 / 18
2 / 16
3 / 20
4 / 10
5 / 22
6 / 14
Total / 100













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1. [18 points] A 0.00145 mole sample of solid naphthalene (C
10
H
8
) is completely
combusted with excess O
2
(g) in a bomb calorimeter. As a result of the complete
combustion of this sample, 7.469 kJ of heat is released to the rest of the
calorimeter - resulting in a temperature increase of 4.53C.

(a) Determine the heat capacity of the calorimeter (C
calorimeter
= C
bomb
+ C
water bath
)
in kilojoules per C. Show all work.







C
calorimeter
kJ/C
(b) Using the same calorimeter as in (a), a 0.00120 mole liquid sample of palmitic
acid (C
16
H
32
O
2
) is completely combusted in excess O
2
(g) via:
C
16
H
32
O
2
(l) + 23 O
2
(g) ------> 16 CO
2
(g) + 16 H
2
O(l) .
As a result of complete reaction, the temperature of the calorimeter and contents
changes from an initial value of 25.00C to a final value of 32.28C. Determine the
enthalpy energy change for the combustion of one mole of liquid palmitic acid
in kJ at 25C. [If you could not arrive at an answer to part (a), assume that
C
calorimeter
is 2.50 kJ/C.]






Enthalpy change for combustion at 25C kJ/mole palmitic acid

(c) Assuming that your answer from (b) was also at standard conditions, use it - along with
the Useful Information, as needed - to determine !H
f,298
(palmitic acid,liquid) in
kJ/mole.






!H
f,298
(palmitic acid, liquid) kJ/mole
Page 3

2. [16 points] At 25C and 1 atmosphere, consider the gas phase combustion reaction.
The balanced reaction is:

2 H
2
(g) + O
2
(g) ------> 2 H
2
O(g)

The standard free energy change at 25C for the above reaction, as written, is - 457.1 kJ.
Showing all work clearly and carefully, determine:

(a) The !H
rxn
in kJ/mol of rxn at 298 K.



















!H
rxn
kJ/mol

(b) The standard molar entropy of O
2
(g) in J/mol-K at 298 K.





















Standard molar entropy of O
2
(g) J/mol-K

(c) With increasing temperature, this reaction becomes (circle one)

MORE SPONTANEOUS LESS SPONTANEOUS







Page 4

3. [20 points] A 0.120 mol sample of laughing gas (N
2
O) is placed in a cylinder fitted
with a movable frictionless piston. This gaseous sample - initially at volume
V
i
= 6.00 L - has a pressure of 0.750 atm - identical to the external pressure. The
gaseous sample is initially at temperature T. This sample - which is thermostatted
with the surroundings- undergoes a compression to a final volume V
f
, for which the
system has a pressure of 5.00 atm. This process is carried out along two different paths
A & B - described below.

Path A: A two-step path as follows:
Step I: The external pressure is increased to 1.50 atm and is held constant at this
value while the volume change takes place. Step I involves a volume
change from V
i
to V
1
.
Step II: The external pressure is increased to 5.00 atm and is held constant at this
value while the volume change takes place. Step II involves a volume
change from V
1
to V
f
.
Path B: The compression occurs isothermally and reversibly.

(a) Determine the following: V
1
(in L), V
f
(in L), overall w (in J) for path A, overall w (in J)
for path B. Also, sketch both paths A and B on the provided axes. Be sure to: clearly
label all volumes (in L) on your diagram; clearly label the work for each step (w
I
& w
II
)
of path A on your diagram; and clearly label how the overall work for path A and the
overall work for path B are related.


V (L)
P
external

(atm)
0
1.50
5.00
0
0.750
























continued on next page

Page 5

(3a) continued work for (a) - as needed















V
1
L ; V
f
L


w
overall, path A
J ; w
overall, path B
J

(3b) For both paths A and B, determine the temperature, T (K) of the system in the
final state, the overall !E and the overall q. Show your work/reasoning. Express
your answers in J.



























T K

!E
overall, path A
J q
overall, path A
J

!E
overall, path B
J q
overall, path B
J

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4. [10 points]
This type of problem will not be on exam 1






















5. [22 points] One mole of carbon tetrachloride, CCl
4
(g), is cooled from 400 K to 300 K at
a pressure of 1 atm. The heat capacities at constant pressure for the liquid and gas are
131 and 110 J/(mol K), respectively. At T
bp
and 1 atm, the heat of vaporization is + 29.8 kJ /
mol and the change in entropy is 85.25 J/(mol K).

(a) Determine the boiling point (T
bp
) at 1 atm.





Boiling point

(b) Determine the change in enthalpy in kJ for the cooling.












Change in enthalpy kJ

(c) Determine the change in internal energy in kJ for the cooling.











Page 7


Change in internal energy kJ

(d) Calculate the change in entropy in J/K for the cooling.



















Change in entropy J/K


6. [14 points] Short answers and true/false.


(a) Per mole, the combustion of ethanol results in a greater enthalpy change than the
combustion of octane.


True or False (Circle one)


(b) Rank the molar heat capacities at constant pressure for nitrogen, helium and ethane at 298K. (2pts)


(c) The enthalpy change of formation for C(s,diamond) at 298K and 1 atm is

zero or 1.9 kJ / mol or -1.9 kJ / mol (Circle one)


(d) What is the entropy for three identical molecules evenly distributed (1 molecule in each bulb) in a
three bulb flask __________________. (2 pts)

(e) The direction of a reaction is determined by the _______ law of thermodynamics .

(f) Identify two effects that the increase in green house gases has had on the earth. (2 pt)

(g) The laws of thermodynamics were discovered mainly during what period.

1800-1850 or 1850 1900 or 1900 - 1950 (Circle one)

(h) In the presence of water, the conversion of ATP to ADP and H
2
PO
4
-
results in stronger phosphorus
oxygen bonds

True or False (Circle one)


(i) If two blocks at the same temperature are joined in a well-insulated container, the entropy of the
universe increases. Briefly, use the relationship between heat and entropy to justify your answer.
Page 8

(2 pts)

True or False (Circle one)



(j) Endothermic processes or chemical reactions can never be spontaneous.

True or False (Circle one)


















Possibly Useful Information

R = 0.0821
L atm
mole K
= 8.314
J
mole K
= 1.987
cal
mole K


PV = nRT ; For a monatomic ideal gas: C
v
=
3
2
R

1 L-atm = 101.33 J ; 1 cm
3
= 1 mL

Right-hand side of some possibly useful equations (Note - two (2) columns):

= q + w = C!T = mc!T = n C !T

= -P
ext
!V = C
v
+ R

= n C
v
!T = n C
p
!T

= !E + !(PV) = !E + !n
g
RT
= q
P
= q
V

= -
!
"
V
i
V
f
P
ext
dV =
!
#
"
initial
final
dq
rev
T

= nRTln
$
%
&
'
(
)
V
f
V
i
= k
B
ln*

= H - TS = !H - T!S

=
!H
T

= n C
P
ln
$
%
&
'
(
)
T
f
T
i
= nRln
$
%
&
'
(
)
V
f
V
i


Thermochemical data at 298 K*:
Substance +H
o
f

$
&
'
)
kJ
mole
S
$
&
'
)
J
mole K

H
2
(g)* ????? 131.0
O
2
(g)* ????? ?????
Page 9

H
2
O(s) -291.8 48.0
H
2
O(l) -285.8 70.0
H
2
O(g) ???? 189.0
CO
2
(g) -393.5 213.6
NH
3
(g) -46.20 ?????
*The standard state form of the element.


Information about water:
!H
vaporization
= +44.00 kJ / mole at 25C
c
P
(liquid) = 75 J/K mol
c
P
(gas) = 36 J/K mol
c
s,p
(liquid) = c
s,p
(liquid) = 4.184 J/K g at 25C
density of liquid water = 1.00 g/mL

Bond Dissociation Energies (Enthalpies) (in kJ/mol) at 298 K & Standard Conditions

C-H = 413; C-C = 347; C=C = 614; H-H = 436;
O-O = 146; C-O = 358; C=O = 799; N=O = 607