Peter Atkins • Julio de Paula

Atkins’ Physical Chemistry

Eighth Edition

Chapter 2
The First Law

Copyright © 2006 by Peter Atkins and Julio de Paula

 Homework Set #2

Atkins & de Paula, 8e

Chap 2 Exercises: all part (b) unless noted
2, 3, 4, 7,
8, 12, 13, 15
19, 21, 23, 25
Fig 2.1 Types of Systems
Fig 2.2 Comparison of Adiabatic
and Diathermic Systems for
Exo- and Endothermic Processes
Fig 2.3 Thermal energy from system to surroundings
Fig 2.4 System does work on surroundings
Equivalent Expressions of the First Law:

• Conservation of energy

• In terms of heat and work

• Formal statement
Internal Energy

• Internal energy, U, is the total kinetic and potential

energy of the molecules in the system

• Approximated by the equipartition theorem:

• Each degree of freedom contributes ½ kT to U

• Degrees of freedom are associated with:

• translation, rotation, and vibration

Kinetic Energy of Translational motion:

EK  1
2
mv 2
x  21 mv 2y  21 mv 2z

• According to the equipartition theorem, the mean trans

energy for one molecule is 3/2 kT

• EK = 3/2 RT for one mole of molecules

• ∴ Um = Um(0) + 3/2 RT

• where Um(0) ≡ molar internal energy at T = 0

 Fig 2.5 Rotational modes of molecules and
corresponding average energies at temperature T

Linear Um = Um(0) + 5/2 RT

Nonlinear Um = Um(0) + 3 RT
First Law in terms of conservation of energy:

• The internal energy of an isolated system is constant

• No ‘perpetual motion machine’ can exist

 Waterfall
by M.C. Escher
First Law in terms of conservation of energy:

• The internal energy of an isolated system is constant

• No ‘perpetual motion machine’ can exist

First Law in terms of heat and work:

• ΔU = q + w (Internal energy is a state function)

• i.e., heat and work are equivalent ways of changing U

 Illustration of change in
internal energy, ΔU,
as a state function.

Formal Statement
of First Law:

The work needed to change an

adiabatic system from one state
to another is the same however
the work is done.
Fig 2.6 General expansion work

• Focus on infinitesimal
changes

• ΔU = q + w becomes

dU = dq + dw

When gas expands:

dw  Pex dV
f


w   Pex dV
i
 Irreversible expansion

Fig 2.7 Work done by a gas

when it expands against a
constant external pressure


w   Pex dV
i
f


 Pex dV   Pex ( Vf  Vi )
i

w  Pex ΔV
 Reversible expansion
Fig 2.8 Work done by a gas
when it expands isothermally
against a non-constant external
pressure.

• Set Pex = P at each step of

expansion

• System always at equilibrium

f


w   Pex dV
i

• Since Pex is not constant, it

can’t be brought out
 Isothermal reversible expansion
f


w   Pex dV
i

• Since Pex is not constant, it can’t be brought out

• However, Pex depends on V, so substitute using PV = nRT

f
dV
w  nRT
V 
i
Vf
 nRT ln
Vi