Physical Chemistry

Problems and exercises

José Mauricio Rodas Rodríguez

Copyright
c 2019 José Mauricio Rodas R.

MAURICIO . RODAS @ UCALDAS . EDU . CO

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First edition, October 2019

 Contents

I Part one
1 The First Law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.1 Problems 7

References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Books 9
I
Part one

1 The First Law of Thermodynamics . . . . . . 7

1.1 Problems

References . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
Books
 1. The First Law of Thermodynamics

1.1 Problems
Problem 1.1 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 2.55x106 L/s.
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 2.55x106 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 hydroelectric power plants
beyond the falls. These plants generate 4.4x109 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.)
Problem 1.2 One mole of He gas with CV,m = 3R/2 essentially independent of temperature
expands reversibly from 24.6 L and 300 K to 49.2 L. Calculate the final pressure and
temperature if the expansion is:
a). isothermal
b). adiabatic
c). Sketch these two processes on a P −V diagram.
Problem 1.3 For a certain perfect gas, CV,m = 2.5R at all temperatures. Calculate q, w, ∆U,
and ∆H when 2.00 mol of this gas undergoes each of the following processes:
a). a reversible isobaric expansion from (1.00 atm, 20.0 dm3 ) to (1.00 atm, 40.0 dm3 )
b). a reversible isochoric change of state from (1.00 atm, 40.0 dm3 ) to (0.500 atm, 40.0
dm3 )
c). a reversible isothermal compression from (0.500 atm, 40.0 dm3 ) to (1.00 atm, 20.0
dm3 )
d). Sketch each process on the same P −V diagram and calculate q, w, ∆U, and ∆H for a
8 Chapter 1. The First Law of Thermodynamics

cycle that consists of steps (a), (b), and (c).

Problem 1.4 What pressure difference must be generated across the length of a 15 cm
vertical drinking straw in order to drink a water-like liquid of mass density 1.0 g/cm3 :
a). on Earth
b). on Mars?
Problem 1.5 Exhalation of air during breathing requires work because air must be pushed
out from the lungs against atmospheric pressure. Calculate the work of exhaling 0.50 L of
air.
Problem 1.6 How much metabolic energy must a bird of mass 200 g expend to fly to a
height of 20 m? Neglect all losses due to friction, physiological imperfection, and the
acquisition of kinetic energy.
Problem 1.7 We are all familiar with the general principles of operation of an internal
combustion reaction: the combustion of fuel drives out the piston. It is possible to imagine
engines that use reactions other than combustions, and we need to assess the work they
can do. A chemical reaction takes place in a container of cross-sectional area 100 cm2 ; the
container has a piston at one end. As a result of the reaction, the piston is pushed out through
10.0 cm against a constant external pressure of 100 kPa. Calculate the work done by the
system.
Problem 1.8 The heat capacity of air is much smaller than that of water, and relatively
modest amounts of heat are needed to change its temperature. This is one of the reasons why
desert regions, though very hot during the day, are bitterly cold at night. The heat capacity of
air at room temperature and pressure is approximately 21 JK −1 mol −1 . How much energy is
required to raise the temperature of a room of dimensions 5.5 m x 6.5 m x 3.0 m by 10 ◦ C?
If losses are neglected, how long will it take a heater rated at 1.5 kW to achieve that increase
given that 1W = 1Js−1 ?
Problem 1.9 The pressures deep within the Earth are much greater than those on the surface,
and to make use of thermochemical data in geochemical assessments, we need to take the
differences into account.
a). Given that the enthalpy of combustion of graphite is -393.5 kJmol −1 and that of
diamond is -395.41 kJmol −1 , calculate the standard enthalpy of the C(s, graphite) −−→
C(s, diamond) transition.
b). Use the information in part (a) together with the densities of graphite (2.250 g/cm3 )
and diamond (3.510 g/cm3 ) to calculate the internal energy of the transition when the
sample is under a pressure of 150 kbar.
Problem 1.10 A typical human produces about 10 MJ of energy transferred as heat each
day through metabolic activity. If a human body were an isolated system of mass 65 kg with
the heat capacity of water, what temperature rise would the body experience? Human bodies
are actually open systems, and the main mechanism of heat loss is through the evaporation of
water. What mass of water should be evaporated each day to maintain constant temperature?
Problem 1.11 How many meters of stairway could a 70 kg man climb if all the energy
available in metabolizing an 11 g spoonful of sugar to carbon dioxide and water could be
converted to work?
Problem 1.12 The average surface pressure at sea level on Earth is 1 atm. Calculate the
average atmospheric column density (kg/m2 ) above the ocean, assuming g = 9.81 m/s2 .
(The atmospheric column density is the mass of an atmospheric column with an area of 1 m2
that extends from Earth’s surface to the top of the atmosphere.)
 References

Books