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Winter 2009 Chemistry 452

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First Examination
February 4, 2009
First Page: Useful information and equations:

Law IA: U q w = +
Law IB:
( , )
V T
U U T V
U U
dU dT dV
T V
=
| | | |
= +
| |

\ \

H U PV = +
Heat Capacity
V P
V P
U H
C and C
T T
| | | |
= =
| |

\ \

Work:
ext ext
w P V or w P dV = =
w mgh and w IQt = =
Kinetic Energy:
2
2
mv
=
Isothermal Reversible work:
ln
f
i
V
w nRT
V
| |
=
|
\

PV Const =
Adiabatic Reversible work: w PdV =
( )
,
,
; where
P m
V m
C
P V Const
C

= =
Integral Identity:
f
i
x
y x
Z
Z dx
x
| |
=
|


( ) ( ) ( ) d yz d y d z
z y
dx dx dx
dx dy dx
dz dz dy
= +
=
Equations of State (EoS)
I.G.:
m
PV RT =
, , P m V m
C C R = +
V P
U C T and H C T = =
VdW EoS:
2
m m
RT a
P
V b V
=


Thermodyanamic EoS
T V
U P
T P
V T
| | | |
=
| |

\ \


Cyclic rule:
1
y x
z
dx dz dy
dy dx dz
| |
| | | |
=
| | |
\ \
\


Reaction Enthalpies
,
, ,
o o
rxn i f i
i
o
i i i i
P rxn i P i
i
o o
rxn
H H
dn n n dx
C C
H H dx

=
= =
=
=


Constants:
8.314 /
0.082 /
298.13 2.48 /
1 4.18
1 4.18
R J mol K
R L atm mol K
R kJ mol
Cal kJ
cal J
=
=
=
=
=

5
1 10 bar Pa =
( ) ( ) 273.15 T K T C = +
2
9.8
sec
m
g =
Winter 2009 Chemistry 452
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Name ______________________________
ID____________

Show your work throughout, and always show units for computed quantities

Q1) Given the heats of formation and Heat Capacities of the following substances,
Substance
o
f
H kJ/mol
o
P
C J/mol-K
( )
2
O g
0.0 29.4
( )
2
CO g
-393.5 37.1
( )
2
H O l
-285.8 75.3
( )
6 12 6
C H O s
-1273.0 219.2
The most basic form of energy consumption people do is burn sugar for energy. The
atmospheric pressure is 1 Bar and body temperature is 37
0
C. The central chemical
equation for this process is:
( ) ( ) ( ) ( )
6 12 6 2 2 2
6 6 6 C H O s O g CO g H O l + +
a) What is the standard enthalpy of this reaction as written at 298K, ( ) 298
o
rxn
H K ?
{ } 6 393.5+6 285.8 1 1273.0 6 0 2.8
o
rxn
MJ
H
mol rxn
= =




b) The standard reference temperature is different from body temperature. Do we get
more (or less) energy by burning the sugar in our bodies as opposed to standard
temperature? [Be sure to show the computation that bolsters your conclusion.]

{ }
,
6 37.1 6 75.3 1 219.2 6 29.4 280 / 0
P Rxn
C J mol K = + = >
( ) ( )
,
o
rxn rxn o P Rxn
H T H T C T = +
Because the net heat capacity is positive, and DT>0, the heat of reaction will be positive
or less exothermic. So we will get less energy from the reaction, as a result of doing it at
a higher temperature.

c) The molecular weight of glucose is 180g/mol, how many Calories (kcal) do we get
from this reaction per gram of glucose?

6
3
3 3
1 1
2.8 10 1
180 4.18
2.8 10
10 3.7 10 3.7
180 4.18
o
rxn
J mol rxn mol cal
H
mol rxn mol glucose gram J
cal Cal
g g

= = =



The minus sign can be omitted because we know it is energy we get from the reaction, so
the reaction is exothermic.
Winter 2009 Chemistry 452
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Q2) A typical soft drink (12 ounce, Oz.) contains 40 grams of glucose.

a) How much energy do we obtain from a single soft drink? [You can assume the burning
is done under standard conditions.]
40 3.7 148 / Cal soft drink =
b) Many times we add ice to cool a soda. Two ice cubes weights about 1.5 ounces. How
cool would the (12 ounce) soda be after adding the ice, assuming the soda started at
25
o
C? The heat capacity of water is 1 cal/gram/degree (thats how a calorie was defined)
and the latent heat of ice is 80 cal/gram. [16 ozs is one pound, and 1kg is 2.2 pounds.]

The soda drops in temperature from Tw=25C to the final temperature T, the ice melts
with the heat of melting (which is positive, as melting is endothermic) and the water of
the ice cubes warm to the final temperature from the Tice which is 0C. All heats are kept
in the container (it is adiabatic) so the total heat is zero.
( ) ( )
, , ,
0
Soda P g w Ice f g Ice P g Ice
H m C T T m H m C T T = = + +
3
,
3
1.5 1
1 1 10 42.6
16 2.2
12 1
1 10 341
16 2.2
P g Ice
Soda
kg g
cal
C m lb g
gK lb kg
kg g
m lb g
lb kg
= = =
= =


( )
( ) ( )
( ) ( )
( )
( )
, , ,
, , ,
,
,
25
0
0 25
25
25
25 341 42.6
Ice w Ice Ice w w Ice
Soda P g w Ice f g Ice P g Ice
Soda P g Ice f g Ice P g
Soda Soda Ice Ice f g
Soda Ice f g
Soda Ice
T T T T T T T T T T T T T
H m C T T m H m C T T
m C T m H m C T
m m m T m H
m m H
T
m m
= + = =
= = + +
= + +
= + +


= =
+ ( )
80
13
341 42.6
K =
+

The final temperature then is 13 degrees C, because the rise is 13K, and the start point is
0C, the freezing point of ice. A mass of ice, a bit over 12% of the mass of the soda,
cooled the soda half way to freezing.

Winter 2009 Chemistry 452
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c) Your legs can easily push 100 pounds (60 kg) up and down. Assuming the leg
extension is about 2 feet (0.7 meters), how many times of pushing 100 pounds would you
need to burn off the energy from the soft drink (in part a of this question)?

( )
3
3
0
148 4.18 10 60 9.8 0.7
148 4.18 10
1, 500
60 9.8 0.7
gas
PV RT n
H J U w Nmg h N
N reps
= =
= = = = =

= =



d) Lets consider the basal level of energy consumption by just breathing. In breathing
we consume about 0.01 moles of oxygen per minute. Assuming that the oxygen is used
to burn glucose, how much energy do we consume per hour, just breathing? [Use results
from Q1) a]

2
2
2
0
2.8
0.6 280
6
min
0.01 60 0.6
min
rxn
O
O
O
H MJ
kJ
U n
hr
moles moles
n
hr hr

= = =
= =





e) If you sit around and drink the can of soda (above) your body will convert the sugar to
fat. Neglecting the energy of conversion, but noting that fats have energy of 9 Cal/gram
as opposed to sugars (which have the amount from above) how much weight would you
gain if the soda were converted to body fat?


3.7
40 * 16.
9
Cal
g sugar
m g sugar g fat
Cal
g fat

= =


So you dont gain weight directly by the sugar, but get about the weight because it is
converted to fat. Of course some is lost in just converting sugar to fat (and burning the fat
to get energy).
Winter 2009 Chemistry 452
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Q3) One mole of an ideal gas, for which
,
5
2
V m
C R = undergoes two successive changes
in state. 1) From 25C at 2 Atm, the gas expands isothermally against a constant
pressure of .5 atm to twice its initial volume. 2) At the end of the previous step the gas is
cooled at constant volume from 25C to -40C.

a) Calculate q, w, U and H for the first step

Isothermal
1
2 1 1 1 1
1
0 0
0.5 12 6 600
0.08 298
2 2 12
2
600
V P
ext
U q w C T H C T
q w P V Atm J
nRT
V V V V V V
P
w J
= + = = = =
= = = = =

= = = = = =
=




b) Calculate q, w, U and H for the second step

Cool at constant Volume

5 5
2 2
7
2
0
0
1 8.3 65 1.35
1 1.9
1.35
V
P
V
w
U C T R T kJ
H C T R T kJ
q U kJ
=
=
= = = =
= = =
= =


Winter 2009 Chemistry 452
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Q4) a) Using the Thermodynamic equation of state, evaluate
T
U
V
| |
|

\
for the van der
Waals gas.


2
2
2 2 2
V m m m
T V m m m m
RT a P R
P
V b V T V b
U P RT RT a a an
T P
V T V b V b V V V
| |
= =
|

\
| | | | | |
= = = =
| | |

\ \
\


b) Assume 5 moles of a van der Waals gas is allowed to expand isothermally, initially at
2 Atm, from liter to 5 liters. This van der Waals gas (similar to oxygen) is described
by
2
2
0.003 2
atm
b and a
mol
mol
= =

, and
,
5
2
V m
C R = . What is the change in the
internal energy of the gas for this process?

{ }
2 2
1 1
5 5
2 2 2
2
2 1 .5 .5
2
2
2
1 1 1
1
2 .2
2
2 5 1.8 90 9
V V
T V V
U
U dV an dV an an
V V V V
atm
a
mol
U Atm kJ
= =
= =
| |
= = = =
`
|

\
)
=
= = =





c) Compare this result with that of an ideal gas.

The energy increased as the volume went up. For an ideal gas there would be no change.


d) Explain why the change in energy has the sign that it does.

The internal energy increased because the mean distance between molecules increased.
Therefore, the stable interactions among the gas molecules were broken or disrupted.
This is the equivalent of bond breaking, which is endothermic, but it is a small effect, 9
kJ.