1

CH 342 Second Midterm

Tuesday, March 4, 2008





Name: ___________________________ ID# ____________________________



The exam has 7 different pages (including this one) and 6 different questions.




1) _________________ (40 pts)

2) _________________ (30 pts)

3) __________________ (35 pts)

4) __________________ (40 pts)

5) ___________________ (25 pts)

6) ___________________ (30 pts)



Total: _____________/200 pts
2
1) (a) Use the ideal gas law to obtain the three functions P = f (V,T), V = g (P,T), and
T = h (P,V). Show that the cyclic rule 1 =

V P T
P
T
T
V
V
P
is obeyed. 15 points
(b) Some of the general relations between partial derivatives can be illustrated more
explicitly by taking the van der Waals equation of state. First calculate
V
P
T

for this
equation. Next, confirm the relation
z
y
x z
x
y

1
, and then go on to confirm the
validity of the cyclic rule. 25 points Total : 40 points
(a)
nR
PV
T
P
nRT
V
V
nRT
P = = = ; ;

nR
V
P
T
P
nR
T
V
V
nRT
V
P
V
P
T
=

; ;
2


1
2
= =

PV
nRT
nR
V
P
nR
V
nRT
P
T
T
V
V
P
V P T


(b)
( )
( ) ( )
( )
( ) ( )
( )
( )
( )
1 Therefore,
2 2 1
2 2
1 that show to need we relation cyclic the For
1
) Therefore
.
3
3
2
3
2
3
2
2
2
2
2
=

= +

=
=
P
T
V
P T
V
P
P
T
P T
V
V
V
V
T
V
P
P
T
T
V
V
P
P
T
nb V
RV
an
nb V
T
nb V
RV
na
RV
na
nR
P
T
V V
T
nb V
nb V
V
a n
nb V
P
V
a n
nb V
nRT
V
P
T
V
V
P
P
T
T
P nR
nb V
P
T
nb V
RV
na
nb V
nR
P
T
RV
a n
nb V
nRT
P

3
2) Calculate w, q, H, and U for the process in which 1 kg of water undergoes the
transition H
2
O (l, 373 K) H
2
O (g, 460 K) at 1 bar pressure. The volume of liquid water
at 373 K is 1.89 10
5
m
3
mol
1
and the volume of steam at 373 and 460 K is
3.03 and 3.7410
2
m
3
mol
1
, respectively. For steam, C
P,m
can be considered constant
over the temperature interval of interest at 33.58 J mol
1
K
1
. 30 points



n = 1 kg / 18.02 g mol
-1
= 55.5 mol

q = H = nH
vaporization
+ nC
P,m

steam
T

= [40656 J + 33.58 J mol
-1
K
-1
x (460 K 373 K)] x 55.5 mol = 2.42 x 10
6
J

w = -P
ext
V = -[(55.5 x 3.03 x 10
-2
m
3
55.5 x 1.89 x 10
-5
m
3
) + (55.5 x 3.74 x 10
-2
m
3
-
55.5 x 3.03 x 10
-2
m
3
)] x 10
5
Pa

= - 168054 J 39405 J = - 2.075 x 10
5
J

U = w + q = 2.42 x 10
6
2.075 x 10
5
J = 2.21 x 10
6
J






















4
3) The isothermal compressibility,
T
P
V
V

=
1
, for lead (Pb) is 2.3 x 10
-6
atm
-1
. A
cube of lead of side 10 cm at 25C is to be inserted in the keel of an underwater
exploration video camera, and its designer need to know the stress in the equipment.
Take the mean density of sea water as 1.03 g cm
-3
and the gravitational acceleration
uniform at g = 9.81 m s
-2
.
(a) Calculate the change in volume of the cube at a depth of 1000 m, disregarding the
effect of temperature. 15 points
(b) Given that the linear thermal expansion coefficient,
P
T
l
l

=
1
, of lead is
2.89 x 10
-5
K
-1
, and the temperature where the camera operates is -5C, calculate the
volume of the block taking also the temperature into account. 20 points
Total: 35 points

(a) The pressure of a column of fluid is given by P = gh, with the density of the
fluid, g is the gravitational acceleration, and h is the height of the column. The
pressure at a depth of 1000 m is
volume. initial its of 0.02% or cm 227 . 0
) atm 1 atm 7 . 99 ( ) cm 10 )( atm 10 x 3 . 2 ( have, we for formula the From
. atm 7 . 99
Pa 101325
atm 1
) Pa 10 x 01 . 1 (
g 1000
kg 1
m 1
cm 100
m) (1000 ) s m (9.81 ) cm g 03 . 1 (
3
3
1 6
7
3
2 -
3 -
=
= =
=

=

P V V
P


(b) The change in the length of one side of the cube is
l = lT
= (2.89 x 10
-5
K
-1
) (10 cm) (268 K 298 K)
= -8.67 x 10
-3
cm
V = (l + l)
3
l
3
= (10 cm 8.67 x 10
-3
cm)
3
(10 cm)
3
= -2.60 cm
3

The change due to temperature is much greater than the change due to the pressure.
V
total
= -2.83 cm
3

so V
f
= V
i
+ V = (10 cm)
3
+ (-2.83 cm
3
) = 997.17 cm
3
.

5
4) Methane can be described by the van der Walls equation of state, with a = 0.232 Pa m
6

mol
-2
and b = 4.33 x 10
-5
m
3
mol
-1
. Assume that the enthalpy is given by the formula
P
RT
a
b T R C H H
m V
)
2
( ) (
, 0
+ + + = , with H
0
a constant and C
V,m
= 27.0 J K
-1
mol
-1
.

(a)

Calculate (H/T)
P
and (H/P)
T
. Compare to the values for an ideal gas. 12 points
(b) The gas, initially at (P
1
, T
1
) is pushed through a throttle to a final state at (P
2
, T
2
), with
P
2
< P
1
. Show that a cooling (T
2
< T
1
, Joule-Thompson effect) of the gas can be obtained
whatever the final pressure P
2
, but there is a maximum initial temperature T
limit
above
which there is no cooling. Give its numerical value for methane. 16 points
(c) What should be the initial pressure P
1
of methane if we want to reach T
2
= 120 K from
T
1
= 300 K, with an output at atmospheric pressure? 12 points

Total 40 points

(a) (H/T)
P
= C
P,m
= C
V,m
+ R + 2aP/RT
2
, while for an ideal gas C
P,m
= C
V,m
+ R.
(H/P)
T
= (b 2a/RT); for an ideal gas the value is zero.
(b) -(H/P)
T
= (2a/RT b) = C
p,m

J-T
. Since

J-T
is independent of the gas pressure,
cooling effect can be obtained for whatever final pressure P
2
. However, at
temperature T = T
limit
,
J-T
= 0 and above that temperature there will be heating on
expansion.
T
limit
= 2a/Rb = (2 x 0.232) / 8.314 x 4.33 x 10
-5
= 1289 K
(c) For isoenthalpic process, dH = C
p,m
dT C
P,m

J-T
dP= 0 or T = P
J-T
(120 K 300 K) = -(P
1
101325 Pa) x
J-T


J-T
= (2a/RT b) / C
p,m
= 3.76 x 10
-6
K/Pa
P
1
= 47.97 x 10
6
Pa = 473.3 atm.







6
5) The standard enthalpy of the hydrogenation of propene in the reaction CH
2
:CH.CH
3
+
H
2
CH
3
.CH
2
.CH
3
is -124 kJ mol
-1
. The standard enthalpy of the oxidation of propane
in the reaction CH
3
.CH
2
.CH
3
+ 5O
2
3CO
2
+ 4H
2
O is -2222 kJmol
-1
. Additionally, the
standard enthalpy of the reaction H
2
+ 1/2O
2
H
2
O is -286 kJmol
-1
. Find the standard
enthalpy of the combustion reaction of propene. 25 points



The enthalpies of the reaction may be found by adding and subtracting the appropriate
reactions.
We require the enthalpy of the reaction
C
3
H
6
(g) + 9/2O
2
(g) 3CO
2
(g) + 3H
2
O (l), H
o
reaction

The reactions given are:
(a) C
3
H
6
(g) + H
2
(g) C
3
H
8
(g), H
o
reaction
(a)

= -124 kJ mol
-1

(b) C
3
H
8
(g) + 5O
2
(g) 3CO
2
(g) + 4H
2
O (l), H
o
reaction
(b)

= -2222 kJ mol
-1

Note that (a) + (b) is the reaction
C
3
H
6
(g) + H
2
(g) + 5O
2
(g) 3CO
2
(g) + 4H
2
O (l),
and so if we also include
(c) H
2
+ 1/2O
2
H
2
O H
o
reaction
(c)

= -286 kJ mol
-1
we can obtain the required reaction as (a) + (b) (c). It follows that
H
o
reaction
= H
o
reaction
(a) + H
o
reaction
(b) - H
o
reaction
(c)

= (-124 2222 + 286) kJ mol
-1

= -2060 kJ mol
-1






7
6) Damp clothes can be fatal on a mountain. Suppose the clothing you were wearing had
absorbed 1 kg of water, and a cold wind dried it. What heat loss does the body have to
make good? How much glucose (C
6
H
12
O
6
) would have to be consumed (energy provided
through the enthalpy of combustion) to replace the loss? Suppose your body did not make
the heat loss, what would your temperature be at the end of the evaporation? (Assume
your estimated body weight (or if you wish use x kg) for the calculation, and that the heat
capacity of the body is the same as that of water). 30 points



H
evap,m
= 44 kJ mol
-1
, n = ( 1 kg)/(18.01 g mol
-1
) = 55.5 mol

q = (44 kJ mol
-1
) x (55.5 mol) = 2.4 x 10
3
kJ

H
c
(glucose) = -2805 kJ mol
-1


2.4 x 10
3
kJ heat can be provided by (2.4 x 10
3
kJ)/(2.8 x 10
3
kJ mol
-1
) = 0.86 mol
glucose, or 155 g.

Assume body mass of 63 kg, then
T = q/C; C = (75.5 J K
-1
mol
-1
) x [(63 kg) / (18.0 g mol
-1
)] = 264 kJ K
-1

T = -(2.4 x 10
3
kJ) / (264 kJ K
-1
) = -9.1 K (-16.4 F)

Therefore T
f
= 82 F for T
i
= 98.4 F.