Atkins & Paula

Physical Chemistry, 8th Ed.

Chapter 2. The First Law

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 The basic concepts
2.1 Work 功, heat 熱, and energy 能量
2.2 The internal energy 內能
2.3 Expansion work 膨胀功
2.4 Heat transactions
2.5 Enthalpy 焓
2.6 Adiabatic changes 絕熱變化

Thermochemistry 熱 化學
2.7 Standard enthalpy changes
2.8 Standard enthalpies of formation
2.9 The temperature-dependence of reaction enthalpies
State functions 状態函數 and exact differentials
2.10 Exact and inexact differentials

2.11 Changes in internal energy

2.12 The Joule-Thomson effect

 Basic concepts of thermodynamics
• Use the principle of conservation of energy — the experimental
observation that energy can be neither created nor destroyed — to
assess the energy changes that accompany physical and chemical
processes
• The means by which a system can exchange energy with its
surroundings in terms of the work it may do or the heat that it may
produce
• The target concept is enthalpy, very useful for keeping track of
the heat output (or requirements) of physical processes and
chemical reactions at constant pressure
• How to establish relations between different properties of a system.
A property can be measured indirectly by measuring others and
then combining their values
• Liquefaction of gases; establish the relation between the heat
capacities of a substance under different conditions
 Chapter 2. Introduction
• The release of energy can be used to provide heat when a
fuel burns in a furnace, to produce mechanical work when a
fuel burns in an engine, and to generate electrical work
when a chemical reaction pumps electrons through a circuit
• In chemistry, we encounter reactions that can be harnessed
to provide heat and work, reactions that liberate energy
which is squandered (often to the detriment of the
environment) but which give products we require, and
reactions that constitute the processes of life
• Thermodynamics, the study of the transformations of
energy, enables us to discuss all these matters quantitatively
and to make useful predictions
 The system is the part of the world
in which we have a special interest,
e.g., a reaction vessel, an engine, an
electrochemical cell, a biological
cell, etc.
The surroundings comprise the
region outside the system and are
where we make our measurements.

Chapter 2. The First Law. P.6

 2.1 Work, heat, and energy
• Work is motion against an opposing force. Doing work is
equivalent to raising a weight somewhere in the surroundings.
e.g., the expansion of a gas that pushes out a piston and raises
a weight. A chemical reaction that drives an electric current
through a resistance also does work, because the same current
could be driven through a motor and used to raise a weight.
• The energy of a system is its capacity to do work. When work
is done on an otherwise isolated system (for instance, by
compressing a gas or winding a spring), the capacity of the
system to do work is increased; in other words, the energy of
the system is increased. When the system does work (when
the piston moves out or the spring unwinds), the energy of the
system is reduced and it can do less work than before.
 An exothermic process is a
process that releases energy as
heat into its surroundings,
combustion;
An endothermic process is a
process in which energy is
acquired from its surroundings as
heat.

Chapter 2. The First Law. P.8

 Molecular interpretation 2.1 Heat

Heating is the transfer of energy

that makes use of disorderly
molecular motion called thermal
motion. The thermal motion of
the molecules in the hot
surroundings stimulates the
molecules in the cooler system to
move more vigorously and, as a
result, the energy of the system is
increased. When a system heats
its surroundings, molecules of the
system stimulate the thermal
motion of the molecules in the
surroundings

Chapter 2. The First Law. P.9

 Work is the transfer of energy
that makes use of organized
motion. The atoms in a spring
move in an orderly way when
wound; the electrons in an
electric current flow in an
orderly direction. When a
system does work it causes
atoms or electrons in its
surroundings to move in an
organized way. Likewise,
when work is done on a
system, molecules in the
surroundings are used to
transfer energy to it in an
organized way.

Chapter 2. The First Law. P.10

 2.2 The internal energy
• The total energy of a system is called its
internal energy, U. The internal energy is the
total kinetic and potential energy of the
molecules in the system. We denote by ∆U the
change in internal energy when a system
changes from an initial state i with internal
energy Ui to a final state f of internal energy
Uf:

An energy of 1 cal is enough to raise the temperature of 1 g of

water by 1°C.
Molecular interpretation 2.2 The internal energy of a gas
The kinetic energy an atom of mass m as it moves through space is:
The equipartition theorem: for a
collection of particles at thermal
equilibrium at a temperature T,
the average value of each
quadratic contribution to the
energy is the same and equal to
½kT

Chapter 2. The First Law. P.32

 The First Law of thermodynamics:
The internal energy of an isolated
system is constant.

2.3 Expansion work: the work

arising from a change in
volume.

(a) The general expression

for work

Chapter 2. The First Law. P.13

(b) Free expansion: expansion against zero opposing force.
pex = 0.

Chapter 2. The First Law. P.14

2.3 Expansion work
(c) Expansion against
constant pressure

If we write the change in

volume as ∆V = V f − V i,

Chapter 2. The First Law. P.15

Comment 2.2

Integral:

f(x)=x2

Chapter 2. The First Law. P.16

 2.3 Expansion work
(d) Reversible expansion
• Reversible change: a change that can be
reversed by an infinitesimal modification of a
variable.
• A system is in equilibrium with its
surroundings if an infinitesimal change in the
conditions in opposite directions results in
opposite changes in its state. e.g., the thermal
equilibrium of two systems with the same
temperature.
 (e) Isothermal reversible expansion
The expansion is made isothermal
by keeping the system in thermal
contact with its surroundings
(which may be a constant-
temperature bath). Perfect gas

Chapter 2. The First Law. P.18

 Example 2.1 Calculating the work of gas production
• Calculate the work done when 50 g of iron reacts with
hydrochloric acid in (a) a closed vessel of fixed volume,
(b) an open beaker at 25°C.
• Answer: (a) w = 0
• Fe(s) + 2 HCl(aq) → FeCl2(aq) + H2(g)
• (b) w = −pex∆V. ∆V = V f − Vi ≈ Vf = nRT/pex, n the
amount of H2.
•
• Fe 55.85 g mol−1
•
• The external pressure?
• Self Test 2.1 Calculate the expansion work when 50 g
of water is electrolyzed under constant pressure at 25°C?
• Correct Answer: (−10 kJ) 2H2O(l) → O2(g) + 2H2(g)
 2.4 Heat transactions
• Generally change in internal energy of a system

where dwe is work in addition to the expansion work,

dwexp

For a measurable change,

計卡儀 Calorimetry is the study of heat
transfer during physical and
chemical processes. A calorimeter
is a device for measuring energy
transferred as heat. The most
common device for measuring ∆U
is an adiabatic bomb calorimeter

Chapter 2. The First Law. P.21

 2.4 Heat transactions (a) Calorimetry

• The change in temperature, ∆T, of the

calorimeter is proportional to the heat that
the reaction releases or absorbs. Therefore,
by measuring ∆T we can determine qV and
hence find ∆U. The conversion of ∆T to qV
is best achieved by calibrating the
calorimeter using a process of known
energy output and determining the
calorimeter constant, the constant C in the
relation
 2.4 Heat transactions (a) Calorimetry

Illustration 2.2 The calibration of a calorimeter

If we pass a current of 10.0 A from a 12 V supply for 300 s, then

from above eqn the energy supplied as heat is
q = (10.0 A) × (12 V) × (300 s) = 3.6 × 104 A V s = 36 kJ
because 1 A V s = 1 J. If the observed rise in temperature is 5.5
K, then the calorimeter constant is C = (36 kJ)/(5.5 K) = 6.5 kJ
K−1.
(b) The heat capacity at constant volume

Chapter 2. The First Law. P.24

 The partial derivative, for
example, if z(x,y) = x2y, then

Chapter 2. The First Law. P.25

 Heat capacity
• Illustration 2.3 Estimating a constant-volume
heat capacity
• The heat capacity of a monatomic perfect gas can
be calculated from the internal energy:
• Um = Um(0) + 3/2RT, so from egn
•

• The numerical value is 12.47 J K−1 mol−1