–1–

CHM222: BASIC PHYSICAL CHEMISTRY

Problem Set - 1.1
Dr. Nisanth N. Nair

Basic Questions:
1. True or false? (a) A closed system cannot interact with its surroundings. (b)
Density is an intensive property. (c) The Atlantic Ocean is an open system. (d) A
homogenous system must be a pure substance. (e) A system containing only one
substance must be homogenous.

2. State whether each of the following systems is closed or open and whether it is
isolated or nonisolated: (a) a system enclosed in rigid, impermeable, thermally
conducting walls; (b) a human being; (c) the planet earth.

3. How many phases are there in a system that consists of (a) CaCO3 , CaO(s), and
CO2 (g); (b) three pieces of solid AgBr, one piece of solid AgCl, and a saturated
aqueous solution of these salts.

4. True or false? (a) One gram is Avogadro’s number of times as heavy as 1 amu. (b)
The Avogadro constant NA has no units. (c) Mole fractions are intensive proper-
ties. (d) One mole of water contains Avogadro’s number of water molecules.

5. For O2 , give (a) the molecular weight; (b) the molecular mass; (c) the relative
molecular mass; (d) the molar mass.

6. A solution of HCl in water is 12.0% HCl by mass. Find the mole fractions of HCl
and H2 O in this solution.

7. True or false? (a) The ratio PV/nT is the same for all gases in the limit of zero
pressure. (b) All ideal gases have the same number of molecules per unit volume
at 25◦ C and 10 bar.

8. For a certain hydrocarbon gas, 20.0 mg exerts a pressure of 24.7 torr in a 500 cm3
vessel at 25◦ C. Find the molar mass and the molecular weight and identify the
gas.

9. For 1.0000 mol of N2 gas at 0.00◦ C, the following volumes are observed as a
function of pressure:
P/atm 1.0000 3.0000 5.0000
V/cm3 22405 7461.4 4473.1

10. After 1.60 mol of NH3 gas is placed in a 1600cm3 box of 25◦ C, the box is heated
to 500 K. At this temperature, the ammonia is partially decomposed to N2 and
H2 , and a pressure measurement gives 4.85 MPa. Find the number of moles of
each component present at 500 K.
 –2–

11. Prove that the equations PV/T = C1 for m constant and V/m = C2 for T and P
constant lead to PV/mT = a constant.

12. a 1.00 L bulb of methane at a pressure of 10.0 kPa is connected to a 3.00 L bulb of
hydrogen at 20.0 kPa; both bulbs are at the same temperature. (a) After the gases
mix, what is the total pressure? (b) What is the mole fraction of each component
in the mixture?

13. A certain mixture of N2 and O2 has a density of 1.185 g/L at 25 ◦ C and 101.3 kPa.
Find the mole fraction of O2 in the mixture. (Hint: the given data and the un-
known are all intensive properties, so the problem can be solved by considering
any convenient fixed amount of mixture)

Zeroth Law of Thermodynamics :

1. True or false? (a) The P–V work in a mechanically reversible process in a closed
system always equals − P∆V (b) The symbol w by the convention we use means
work done on the system by the surroundings. (c) The infinitesimal P − V work
in a mechanically reversible process in a closed system always equals − PdV. (d)
The value of the work w in a reversible process in a closed system can be found
if we know the initial state and the final state of the system. (e) The value of
R2
the integral 1 PdV is fixed once once the initial and final states 1 and 2 and the
R2
equation of state P ≡ P( T, V ) are known. (f) The equation wrev = 1 PdV applies
R2 R2
only to constant-pressure processes. (g) 1 PdV = 1 nRdT for every reversible
process in an ideal gas.

2. For a given change of state, wrev can have any positive or negative value. Consider
a change of state for which P2 = P1 and V2 > V1 . For this change of state, use a
P − V diagram to (a) sketch a process with wrev < 0; (b) sketch a process with
wrev > 0. Remember that neither P nor V can be negative.

3. Specific heats can be measured in a drop calorimeter; here, a heated sample is

dropped into the calorimeter and the final temperature is measured. When 45.0 g
of a certain metal at 70.0◦ Cis added to 24.0 g of water (with c P = 1.00 cal g−1 ◦ C −1 )
at 10.0◦ Cin an insulated container, the final temperature is 20.0◦ C. (a) Find the
specific heat capacity of the metal. (b) How much heat flowed from the metal to
the water? Note: In (a), we are finding the average c P over the temperature range
of the experiment. To determine c P as a function of T, one repeats the experiment
many times, using different initial temperatures for the metal.

4. William Thomson tells of running into Joule in 1847 at Mont Blanc; Joule had
with him his bride and a long thermometer with which he was going to “try for
elevation of temperature in waterfalls.” The Horseshoe Falls at Niagara Falls is
167 ft high and has a summer daytime flow rate of 2.55×106 L/s.
 –3–

(a) Calculate the maximum possible temperature difference between the water
at the top and at the bottom of the falls. (The maximum possible increase
occurs if no energy is transferred to such parts of the surroundings as the
rocks at the base of the falls.)
(b) Calculate the maximum possible internal energy increase of the 2.55×106 L
that falls each second. (Before it reaches the falls, more than half the water of
the Niagara River is diverted to a canal or underground tunnels for use in hy-
droelectric power plants beyond the falls. These plants generate 4.4×109 W.
A power surge at one of these plants led to the great blackout of November 9,
1965, which left 30 million people in the northeast United States and Ontario,
Canada, without power for many hours.)

5. Explain how liquid water can go from 25◦ C and 1 atm to 30◦ C and 1 atm in a
process for which q < 0.

6. The potential energy stored in a spring is 12 kx2 , where k is the force constant of
the spring and x is the distance the spring is stretched from equilibrium. Suppose
a spring with force constant 125 N/m is stretched by 10.0 cm, placed in 112 g of
water in an adiabatic container, and released. The mass of the spring is 20 g, and
its specific heat capacity is 0.30 cal g−1 ◦ C −1 . The initial temperature of the water
and the spring is 18.0◦ C. The water’s specific heat capacity is 1.0 cal g−1 ◦ C −1 .
Find the final temperature of the water.

7. Consider a system enclosed in a vertical cylinder fitted with a frictionless piston.

The piston is a plate of negligible mass, on which is glued a mass m whose cross-
sectional area is the same as that of the plate. Above the piston is a vacuum.

(a) Use conservation of energy in the form dEsyst + dEsurr = 0 to show that for an
adiabatic volume change dEsyst = −mg dh − dKpist , where dh is the infinitesi-
mal change in piston height, g is the gravitational acceleration, and dKpist is
the infinitesimal change in kinetic energy of the mass m.
(b) Show that the equation in part (a) gives dwirrev = − Pext dV − dKpist for the
irreversible work done on the system, where Pext is the pressure exerted by
the mass m on the piston plate.
(c) Suppose the above system is initially in equilibrium with P = 1.000 bar and
V = 2.00 dm3 . The external mass m is instantaneously reduced by 50% and
held fixed thereafter, so that Pext remains at 0.500 bar during the expansion.
After undergoing oscillations, the piston eventually comes to rest. The final
system volume is 6.00 dm3 . Calculate wirrev .
[Note: dEsyst =⇒ system energy and dEsurr =⇒ surrounding energy]

8. State whether each of the following is a property of a thermodynamic system or

refers to a noninfinitesimal process: (a) q; (b) U; (c) w; (d) CV .

9. Calculate the work done during the isothermal reversible expansion of a van der
Waals gas.
 –4–

10. For 2.0 mol of a certain perfect gas, CV,m = 2.5R at all temperatures. Calculate q,
w, and ∆U for a reversible isothermal compression from (0.500 atm, 40.0 dm3 ) to
(1.00 atm, 20.0 dm3 ).
[Note: CV,m =⇒ Heat capacity/mol ]

First Law of Thermodynamics :

1. Note down the intensive/extensive properties from the following : Internal en-
ergy (U), Pressure (P), Volume(V), Temperature(T), Work done(w), Force(F), Area(A),
Length(L), Heat(q), Heat capacity(C), Molar heat capacity (Cm )

2. Calculate the final temperature, and molar heat capacity of Ar, initially at 298 K,
in a reversible adiabatic expansion from 0.50 dm3 to 2.0 dm3 .

3. Calculate the values of q, w and U for a irreversible isothermal expansion of a

ideal gas.

4. Calculate the work needed for a 65 kg person to climb through 4.0 m on the
surface of (a) Earth and (b) moon (g = 1.60 m s−2 )

5. Calculte the work done by 2.5 mol of an ideal gas to expand reversibly and isother-
mally to five times its initial volume at 373 ◦ C

6. This problem finds an approximate expression for Uintermol , the contribution of

intermolecular interactions to U. As the volume V changes at constant T, the av-
erage distance between molecules changes and so the intermolecular interaction
energy changes. The translational, rotational, vibrational, and electronic contri-
butions to U depend on T but not on V. Infinite volume corresponds to infi-
nite average distance between molecules and hence to Uintermol = 0. Therefore
U ( T, V ) − U ( T, ∞) = Uintermol ( T, V ).
R V0
(i) Verify that Uintermol ( T, V 0 ) = ∞ = (∂U/∂V ) T dV, where the integration is at
constant T, and V 0 is some particular volume.
(ii) Show that (∂U/∂V ) T = an2 /V 2 for van der Waals equation of state

an2
 
P+ 2 (V − nb) = nRT
V

(iii) Using the relation (∂U/∂V ) T = an2 /V 2 show that for a van der Waals gas
Uintermol,m = − a/Vm . (This is only a rough approximation since it omits
the effects of intermolecular repulsions, which become important at high
densities.)
(iv) For small to medium-size molecules, the van der Waals a values are typically
106 to 107 cm6 atm mol−2 . Calculate the typical range of Uintermol,m in a gas
at 25◦ C and 1 atm. Repeat for 25◦ C and 40 atm.