MASSACHUSETTS INSTITUTE OF TECHNOLOGY

Department of Chemistry

5.60/20.110/2.772
Fall 2009
Problem Set #1
Due: September 18
HAND IN PROBLEMS 1, 3, 5, 6

Readings: Chapter 1, sections 1.1-1.5, 1.8; chapter 2, all sections

1. The isobaric thermal expansion coefficient of any substance is defined by

! = V
-1
(!V/!T)
p


where V is the volume at pressure p and temperature T. For liquid ethanol,
!=1.04 x 10
-3
+ 1.56 x 10
-6
t + 5.16 x 10
-8
t
2,
where t is the Celsius temperature
(
o
C).

(a) Find V(t)/V(0
o
C) as a function of t for ethanol by integrating the above
expression, and plot V(t)/V(0) versus t over the range 0-50
o
C.
(b) Suppose an ethanol thermometer is calibrated so that it gives correct
ideal-gas readings at 0
o
C and 50
o
C but the scale between these values is assumed
to be linear in the volume. What will the ethanol thermometer read when an
ideal-gas thermometer reads 40
o
C?


2. A bulb filled with nitrogen tetroxide (N
2
O
4
) at 50
0
C and 500 Torr weighs
171.981g. The same bulb weighs 171.217 g when evacuated and 656 g when filled
at 25
0
C with water (density of water is 0.997 at 25
o
C).

(a) Calculate the total number of moles of gas present in the bulb. (Assume
the ideal-gas law.) Also find the ratio of this number of moles to the number
of formula weights of N
2
O
4
. (The "formula weight" is the molecular weight
based on an assumed chemical formula for the substance. In this case, the
formula weight of N
2
O
4
is 92 g. If the gas were in fact all N
2
O
4
molecules, the
desired ratio would obviously be 1.)

(b) On the basis of the dissociation reaction N
2
O
4
(g) = 2N0
2
(g), calculate the
fraction ! of N
2
O
4
that has been dissociated. Note that the number of moles of
N
2
O
4
gas at equilibrium equals (l-!) x (the number of formula weights of N
2
0
4
)
where 1-! is the fraction undissociated.

(c) Calculate the partial pressures of both N
2
O
4
and NO
2
in the bulb.


3. One mole of CO
2
gas is held in a cylinder by a piston subject to an external
applied pressure of 100 atm. The temperature is maintained constant at 65
0
C
by thermal contact with a large heat bath at that temperature.

(a) The external pressure is decreased in three sudden steps: first to 50 atm,
then to 20 atm, then to 1 atm. Assuming CO
2
to be an ideal gas, compute the
work done in this irreversible expansion. Express the answers in Joules.
(b) Compute the work done in a reversible isothermal expansion from 100 atm to
1 atm (again assuming ideal gas behavior).

4. One mole of nitrogen gas at 30
o
C and 1 bar is expanded reversibly and
isothermally to a pressure of 0.2 bar. (a) How much work is done? (b) How
much work would have been done in an expansion against a constant pressure of
0.2 bar? You may assume nitrogen is an ideal gas. Express your answers in
Joules.

5. One mole of an ideal gas at 25 C and 100 bar is allowed to expand reversibly and
isothermally to 5 bar. (a) Write the change in state. (b) Calculate the work , heat,
"U and "H for this change in state.

6. 2.0 moles of molecular hydrogen are contained in a 1.0 L cylinder at 30C.
Calculate the pressure in bar according to the (a) ideal gas law
(b) van der Waals equation. The van der Waals constants for H
2
are a =
0.2476 L
2
bar mol
-2
and b = 0.02661 L mol
-1
. Assuming that the van der
Waals equation gives the right answer, what is the percent error in using
the ideal gas law?