1.

Calculate the work done (in joules) on the system for each of the following
examples. Specify the sign of the work.
a) A box of groceries weighing 10 kg is carried up three flights of stairs (10m total).
w = mgh = (10kg)(9.81m/s
2
)(10m) = 981J
b) A muscle of 1 cm
2
cross section and and 10.0 cm length is stretched to 11.0 cm
by hanging a mass on it. The muscle behaves like a spring that follows Hookes
law. The Hookes law constant for the muscle was determined by finding that the
muscle exerts a force of 5.00 N when it is stretched from 10.0 cm to 10.5 cm.
F = kx k = F/(x-x
0
)
k = 5.00N/(0.105m - 0.100m) = 1.00 x 10
3
N/m
w = k/2(x-x
0
)
2
= [(1.00 x 10
3
N/m)(0.01m)
2
]/2
w = 0.050 J
c) The volume of an ideal gas changes from 1.00 L to 3.00 L at an initial
temperature of 25C and a constant pressure of 1 atm.
w = -P(V
2
- V
1
) = [(-1.00atm)(2L)(8.413J)] / 0.08205L*atm
w = -203J
d) The volume of an ideal gas changes from 1.00 L to 3.00 L at a constant
temperature of 25C, and the expansion is done reversibly for an amount of gas
corresponding to an initial pressure of 1 atm.
Aw = -nRTln(V
2
/V
1
) = P
1
V
1
ln(V
2
/V
1
)
w = -(1.00atm)(1.00L) * ln(3.00L/1.00L) * (8.413J / 0.08205L*atm)
w = -111J

2. Why is it useful for engineers to know the First Law of Thermodynamics?
It is useful to know that energy can neither be created nor destroyed but only
converted from one form to another. This law if very useful to keep and work with
energy balances and to show that a perpetual motion machine is not possible.

3. On your way to Viridian City, you discover the mischievous Team Rocket up to
no good. To stop them, you command your charmander to use flamethrower on
team rockets hot air balloon.

a) If each flamethrower results in 121.6 kJ of heat being transferred to the
balloon, what is the change in volume (V) of the balloon after one
flamethrower? Assume that this process is isothermal and that the balloon is
expanding against a constant external pressure of 1.2 atm.

b) Using the formula H = U + (PV), calculate the change in enthalpy (H).
Compare your answer to the heat transferred per flamethrower (q). Does this
make sense?

c) If the balloon will explode if its volume increases by 9.5 m
3
or more, how many
flamethrowers will it take to pop the balloon and send Team Rocket blasting
away again?

d) If, instead, the air inside of the balloon heats up when hit by a flamethrower,
would you expect it to take more or less flamethrowers to pop Team Rockets
balloon? Explain. (Hint: Consider U when temperature changes)

A) U = q + w, U=0 because isotherm so q=-PV
V = -q/P, q=-121600J so V = -121600J/-121600Pa = 1 m^3

B) Delta H = Delta U + Delta(PV) = 1 m^3 * 1.2atm = 121.6 KJ, which is the same as the
energy transfered by flamethrower. This makes sense because Delta H is defined as
the heat added under constant pressure conditions q
p
.

C)9.5/1 = 9.5 ---> 10 flamethrowers

D) More because Delta U would be positive and no longer zero in the equation Delta U
= q + w. ---> -w = q- Delta U. If Delta U is positive, then w will be smaller and so the
delta V will also be lesser.



4. a) As you walk to class you get caught in a rainstorm and absorb 1.00 L of water
into your clothing. It is windy so that this amount of water is evaporated quickly at
20C, how much heat would be required for this process?

b)If all this heat were removed directly from you (no significant heat was
generated by metabolism during this time), what drop in body temperature would
you experience? You have a mass of 60 kg, and you can approximate the heat
capacity of yourself as equal to that of water.

c) Lucky for you, you had a large lunch. How many grams of sucrose would the
hiker have to metabolize quickly to replace this heat and not change your body
temperature. You can use the heat of reaction at 25C; the reaction is:
C
12
H
22
O
11(s)
+ O
2(g)
CO
2(g)
+ H
2
O
(g)

a) q
p
= H = (1L)(0.9928 kg/L)(2447 kJ/kg) = 2443 kJ
b) T = (2443 kJ)/[60 kg * 4.18 kJ/K kg] = 9.7 K
c) Balance the equation first, get coefficients of 1, 12, 12, and 11
H = 11(-285.83) + 12(-393.51) - (-2222.1) = -5644 kJ/mol
wt. = 2443 kJ * 342.31 g/mol / 5644 kJ/mol = 148.2 g


5. Imagine you have a tube with a length of 10 cm filled with an aqueous
suspension of gold nanoparticles at room temperature (25C). Imagine the
diameter of the nanoparticles to be 10 nm. Lets assume this tube is resting in a
vertical position on a completely vibration-free table for a very long time.
a. Does the concentration of the particles in this tube vary significantly
between the bottom of the tube and the top of the tube? Support your
answer with the relevant calculation. (Hint: Consider the energy of a
particle in a potential field.)
b. The density of water is 1 g/mL and the density of gold is 19.7 g/mL. Do the
same calculation for an aqueous protein solution where the diameter of
the protein is also 10 nm and the density of the protein is 1.37 g/mL.
c. What do we learn from this result with regards to aqueous protein
solutions?
d. What is the reason for this result on a molecular/thermodynamic level?
Fall 2012 Midterm Exam Q8
a) Since the gold nanoparticles are suspended in water, the density difference
between the particle and the water displaced by the particle determines the
potential energy of the particles:
E
potential
= (
p
-
w
) * V
p
* g * h , 0cm < h < 10cm

V
p
= (4/3)r
3
= (4/3)**(5 x 10
-9
m)
3
= 5.236 x 10
-25
m
3


E
potential | h = 0.1 m

= (19300 kg/m
3
- 1000 kg/m
3
) (5.236 x 10
-25
m
3
) (9.81 m/s
2
)
(0.1 m)
= 9.3998 x 10
-21
J
E
potential | h = 0 m
= 0 J

E
potential
= E
potential | h = 0.1 m
- E
potential | h = 0 m
= 9.3998 x 10
-21
J
k
B
= 1.38 x 10
-23
J/K
T = 298 K

N
2
/N
1
= e
-E/(kb T)
= 0.102

Therefore the concentration of gold nanoparticles near the top of the tube is
only around 10% of the concentration at the bottom of the tube. Hence, a
significant difference exists.

b) For the protein molecules we get:
E
potential | h = 0.1 m

= (1370 kg/m
3
- 1000 kg/m
3
) (5.236 x 10
-25
m
3
) (9.81 m/s
2
) (0.1
m)
= 1.9 x 10
-22
J = E
potential


N
2
/N
1
= e
-E/(kb T)
= 0.955
Therefore the concentration of protein at the top is 95.5% the concentration of
protein at the bottom. Less than 5% difference not very significant
difference.

c) Aqueous solutions of water soluble proteins do not typically lead to the settling
of proteins, i.e. proteins remain homogeneously mixed in aqueous solution.

d) The reason for this absence of settling is that the potential difference
compared to k
B
T is large for gold particles and small for proteins.

6. An ideal gas expands reversibly from 1 L to 10 L under reversible, isothermal
conditions. Determine whether the following statements are true or false and
explain:
(a) U=0;
(b) H>U.
Answer:
(a) True: because the internal energy of a gas is only a function of temperature, the
internal energy doesnt change if the temperature doesnt change.
(b) False: for expansions under isothermal conditions, H=U=0 (H=U+PV=U+nRT,
nRT doesnt change so H doesnt change).

7. A sample of 1.00mol perfect gas molecules, initially at 298 K and 1 atm with
Cp,m = (7/2) R is put through the following cycle:
(a) constant-volume heating to twice its initial pressure
(b) reversible, adiabatic expansion back to its initial temperature
(c) reversible isothermal compression back to 1 atm.
Calculate H, U for each step and the overall cycle.
Answer:
(a) The change in entropy is H=U+VP under constant volume. Since the volume is
constant, w=0 so U=q. For this constant volume heating process,
U=q=Cv T=(Cp-R)T=2.5PV=6.2kJ.
Therefore H=2.5PV+(2PV-PV)=3.5PV=8.7kJ.
(b) H=U+(PV)=U+nRT. Again, use the fact that the internal energy is only a
function of temperature, so U= - 6.2kJ. The latter part nRT is
nRT=PV-2PV=-PV= - 2.5kJ.
Therefore, the overall H= - 8.7kJ.
(c) For isothermal expansion/compression of gases, H=U=0.
(d) Using the fact that H is a state function or just simply sum it up, H=0.
Fastest Route:
(a) U=q=Cv T=(Cp-R)T=2.5PV=6.2kJ.
Therefore H=2.5PV+(2PV-PV)=3.5PV=8.7kJ.
(d) Since we have the same initial and final states, the H=U=0.
(c) For isothermal processes, H=U=0.
(b) Simple substraction to get H=-8.7kJ and U=-6.2kJ.

8. What type of calorimeter would you use to measure the heat released during the
combustion of methanol? Make a drawing of the experimental set-up and explain
your choice of calorimeter.
Bomb calorimeter with constant volume or constant pressure calorimeter with a
moveable piston to maintain constant pressure. Drawing should include a thermometer,
insulation, a water bath or some liquid with known heat capacity, and a way to introduce
the reactants (methanol and oxygen).