Study unit 2: The first law of thermodynamics

Chapter 2
The First Law of
Thermodynamics

Atkins’ Physical Chemistry

9th Edition

Peter Atkins • Julio de Paula

 Contents

2.0 Introduction
2.1 Work, heat and energy
2.2 Thermal energy
2.3 The internal energy
2.4 Expansion work
2.5 Heat transactions
2.6 Enthalpy
2.7 Adiabatic change
2.8 Standard enthalpy changes
2.9 The temperature dependence of reaction
enthalpies
 Introduction

This chapter introduces some of the basic

concepts of thermodynamics:
• conservation of energy,
• shows how the principle of the conservation of energy
can be used to assess the energy changes.

Thermodynamics
is the study of the transformations of energy or the
study of heat and other forms of energy involved in
chemical or physical processes.
 Introduction

The basic concepts

In Physical Chemistry, the universe is divided into two parts,
the system and its surroundings.

System + Surroundings = Universe

System Surroundings
 Introduction
.

Thermodynamic System:
The substance under study in
which a change occurs is called
the thermodynamic system (or
just system).

Thermodynamic Surroundings:
Everything else in the vicinity is
called the thermodynamic
surroundings (or just the
surroundings).
 Introduction
The type of the system depends on the characteristics of the boundary that
divides it from the surroundings.

Open system –
can exchange both energy and matter with the surroundings.

Closed system –
exchanges energy but NOT matter with the surroundings

Isolated system –
neither energy nor matter can be exchanged with the
surroundings
 Introduction

• The type of the system depends on the characteristics

of the boundary that divides it from the surroundings.
• Both open and closed systems can exchange energy
with their surroundings.

8
 Work, heat and energy

• The fundamental physical property in thermodynamics is

work.

• Work is the transfer of energy by motion against an

opposing force, dw = –Fdz.

• Heat is the transfer of energy in and out of the system

because of a temperature difference between the system
and the surroundings.

• Energy of a system is the capacity to do work. The

internal energy is the total energy of a system.
 Work, heat and energy

• When the system does work (when the piston moves out), the
energy of the system is reduced and it can do less work than before.

• When the energy of a system changes as a result of a temperature

difference between the system and its surroundings we say that
energy has been transferred as heat.

–PDV
 Work, heat and energy

DU or D E, q, w, and their signs

 Work, heat and energy

Endothermic and Exothermic Processes

Endothermic Process: A chemical reaction or process in

which heat, q is absorbed by the system from the
surroundings. The reaction vessel will feel cool (i.e. lowering
of the temperature of the surroundings).

Exothermic Process: A chemical reaction or process in

which heat, q is evolved by the system to the surroundings.
The reaction vessel will feel warm (i.e. rise in temperature of
the surroundings).
Work, heat and energy
 Thermal energy

• Heating is the transfer of

energy that makes use of Thermal energy
disorderly molecular motion
called thermal motion (TM)

• The TM of the molecules in

the hot surroundings
stimulates the molecules in
the cooler system to move
more vigorously and, hence,
increase the energy of the
system.
 Thermal energy

When energy is transferred to the

surroundings as heat, the transfer
stimulates random motion of the atoms in
the surroundings. Transfer of energy from
the surroundings to the system makes use
of random motion (TM) in the surroundings.

When a system does work, it stimulates

orderly motion in the surroundings. For
instance, the atoms shown here may be
part of a weight that is being raised. The
ordered motion of the atoms in a falling
weight does work on the system.
 State function

A State Function:
Is a property of a system whose
values depend only on the state of
a system, not on the path by
which the system has reached that
state.
 State function

The altitude of a campsite is

a state function.
It is independent of the path
taken to reach it.
 State function

Present State

Cooling Heating

U depends only on the present state of the system and not on the path by which it arrived at that
state.
The internal energy of 50 g of water @ 25°C is the same whether the water is cooled from a higher
temperature to 25°C or warmed from a lower temperature to 25°C
 The internal energy

The internal energy, U is the total Ek and Ep of the

molecules in the system:

∆U is a state function because its value depends on the

current state of the system.
• Changes in molar internal energy, ∆Um, are expressed in
kilojoules per mole (kJ. mol−1)
• 1 electronvolt (1 eV) is defined as the Ek acquired when
an e- is accelerated from rest through a potential
difference of 1 V.
 The internal energy

Changes in Internal Energy

When energy is
exchanged between
the system and the
surroundings, it is
exchanged as either
heat (q) or work (w).

That is, DU= q + w.

 The internal energy

The current definition of the calorie in terms of

joules is;

An energy of 1 cal is enough to raise the

temperature of 1 g of water by 1°C.
 The internal energy

Molecular interpretation of internal energy

• A molecule has a certain number of motional degrees of freedom, such
as the ability to translate (the motion of its centre of mass through
space), rotate around its centre of mass, or vibrate (as its bond
lengths and angles change).
 The internal energy

Molecular interpretation of internal energy

• A molecule has a certain number of motional degrees of freedom, such
as the ability to translate (the motion of its centre of mass through
space), rotate around its centre of mass, or vibrate (as its bond
lengths and angles change).
 The internal energy

Molecular interpretation of internal energy

• Many physical and chemical properties depend on

the energy associated with each of these modes
of motion.
E.g. a chemical bond might break if a lot of energy
becomes concentrated in it.
 The internal energy

The equipartition theorem of classical mechanics is a

useful guide to the average energy associated with each
degree of freedom when the sample is at a temperature.

According to this theorem, the average energy of each

quadratic contribution to the energy is ½(kT). Here k is
the Boltzmann’s constant with the value k = 1.381×10-23
J.K-1.
The mean energy of the atoms free to move in three
dimensions is 3/2(kT) and the total energy of a
monoatomic perfect gas is 3/2(NkT) or 3/2(nRT)
[because N = nNA and R = NAk].
 The internal energy

The ET can also make quantitative predictions about how much energy
will appear in each degree of freedom. Specifically, it states that each
quadratic degree of freedom will on average possess an energy ½kT.

Maxwell-Boltzmann distribution of molecular speeds can be utilized to

determine the average Ek of a particle in a gas and show that it agrees
with the equipartition result.

3
U m (T )  U m (0)  RT (monoatomic gas, translational only) (2.2)
2
Where Um (0) is the molar internal energy at T = 0, when all transitional motion has ceased
and the sole contribution to the internal energy arises from the internal structure of the
atoms.

This equation shows that the internal energy of a perfect gas increases
linearly with temperature.
 The internal energy

 When the gas consists of

polyatomic molecules, we take into
consideration the effect of rotation
and vibration.
 A linear molecule (example, N2 and
CO2) can rotate around two axes
perpendicular to the line of the
atoms, so it has two rotational
modes of motion each contributing
a term ½kT to the internal energy.
 Therefore, the mean rotational
energy is kT and the rotational
contribution to the molar internal
energy is RT.
 The internal energy

3
U m (T )  U m (0)  RT (monoatomic gas, translational only) (2.2)
2
By adding the translational and rotational contributions, we obtain
5
U m (T )  U m (0)  RT (linear molecule, translational and rotational only) (2.3)
2
 The internal energy

 A nonlinear molecule (example,

CH4 or H2O) can rotate around
three axes and, again, each mode
of motion contributes a term ½kT to
the internal energy.
 Therefore, the mean rotational
energy is 3/2(kT) and the rotational
contribution to the molar internal
energy is 3/2(RT).
 The internal energy

3
U m (T )  U m (0)  RT (monoatomic gas, translational only) (2.2)
2
By adding the translational and rotational contributions, we obtain
5
U m (T )  U m (0)  RT (linear molecule, translational and rotational only) (2.3)
2

Therefore, for a nonlinear molecule;

U m (T )  U m (0)  3RT (Nonlinear molecule, translational and rotational only) (2.4)

The internal energy now increases twice as rapidly with

temperature compared with the monoatomic gas.
 Reminder

Test Dates:
Test 1: 26 August 2017
(Next week Saturday)
 . The first law

Formulation of the First Law

General ways to exchange ENERGY

HEAT WORK
lost/gained Done by/on
by system system

q w
Relationship:
DU = q + w
 The first law

Formulation of the First Law

DU = q + w
where
w = work done on a system
q = energy transferred as heat to a system
∆U = change in internal energy

 It has been found experimentally that if a system is isolated from its

surroundings, no change in internal energy occurs.
 This summary of observations is known as the first law of
thermodynamics.
States that the internal energy of an isolated system is constant.
 The first law

Example
If an electric motor produced 15 kJ of energy each second as
mechanical work and lost 2 kJ as heat to the surroundings. What is the
change in the internal energy, ΔU, of the motor each second?
Solution
We need to remember the sign conventions. That is, the motor
produced 15 kJ means a (-) value and the fact that 2 kJ was lost as
heat means a (-) value. Therefore, the change in the internal energy of
the motor each second is;
DU  q  w
DU  2kJ  15kJ  17kJ
 The first law

Example
Suppose that, when a spring was wound, 100 J of work was done on it
but 15 J escaped to the surroundings as heat. What is the change in
the internal energy, ΔU, of the spring?
Solution
We need to remember the sign conventions. That is, 100 J of work was
done on it means a (+) value and the fact that 15 J of energy escaped
the system means a (-) value. Therefore, the change in internal energy
of the spring is;
DU  q  w
DU  100J 15J  85J
 The first law

Heat and Work

The PV Product: (Physical Meaning)
Consider the dimensions of the PV product

PV  ( pressure )  (volume)

 force   These are the

PV     volume
 area  dimensions of work.
 It therefore, means that
PV 
force
 length 3
the PV product
length 2 expresses mechanical
work.
PV  ( force)  (length)
 The first law

Mechanical Work Involving Gases

Mechanical work includes:

 The work required to compress a gas
 The work done by a gas when it expands

This work is often referred to as the PV-work

.
For the reaction
2Na(s) + 2H2O(l )  2NaOH(aq) + H2(g)

–PDV

The H2 gas had to do work to raise the piston.

For the reaction as written at 1 atm, -PDV = -2.5 kJ.
In addition, 368.6 kJ of heat are evolved.
 The first law
Expansion work

Expression for the expansion work

 The work done by a gas on expansion is equal to the product of the external
pressure against which the gas is expanding multiplied by the volume change
the gas undergoes.

Consider an infinitesimal change:

dw   Pext dV
where:
Consider an finite change: dw = work done by the gas
Pext = external pressure
V2
dV = change in volume
w    Pext dV
V1
Let us consider some cases in which the integration can be performed easily.
 The first law

Expansion Work (Finite Change)

1. Free expansion into a vacuum

A gas expands isothermally into an evacuated vessel.

In this case,
dw   Pext dV
dV  0
Therefore: So we can see that when
a gas expands freely into
dw  0 a vacuum, there is no
work done in the
w  0 expansion.
 The first law

2. Expansion against a constant pressure

The external pressure remains constant during the expansion.
Therefore, from V2

w    Pext dV In an expansion:
V1
V2 > V1
If we integrate, we obtain:
Therefore,
w   Pext V2  V1 
V2 - V1 > 0

This equation can also be written as: Consequently,

w   Pext DV w <0

The system does work on the surrounding

 The first law

3. Reversible isothermal expansion against a changing external pressure

Reversible change: A change that can be reversed by an infinitesimal modification

of a variable.

Reversible expansion: Here the external pressure is only infinitesimally less than
the internal pressure (the pressure exerted by the gas) at any instant. Therefore,
we can write,

Pext  Pint
Where Pint is the pressure of the gas.
 The first law

Finding the expression for the This expression can be used to express Pint,
work done (Reversible isothermal expansion) V2
nRT
We consider the equation, w   dV
V1
V R = the gas
V2 Therefore, we can write constant
w    Pext dV V2 n = constant for a
1

given amount of
V1
w  nRT dV gas
We write Pint instead of Pext V1
V T = constant in an
V2 isothermal
w    Pint dV
By integrating, we obtain: process
V1  V2 
In order to integrate, we must be able to
w  nRT ln  
express the pressure of the gas in terms of  V1 
its volume. This can be done by using the This can also be written as,
state equation of the gas. Consider the
case of an ideal gas.
P P1V1  P2V2
nRT w  nRT ln  1 
P   P2 
V
 The first law

4. Adiabatic expansion

Adiabatic change: A change that occurs in a system that is isolated from its
environment, so that no heat may enter or exit the system. Therefore, in an
adiabatic change,

dq  0
Any work done by the
Equation,
system during an
dU  dq  dw
adiabatic change is done
then becomes, at the expenses of the
dU  dw internal energy
 The first law
Example
Calculate the work done when 50.00 g of iron dissolves in hydrochloric acid
at 25°C:
a) In a closed vessel Useful Data:
b) In an open beaker Mass of iron that reacts =
50.00 g
Temperature: 25°C=298
Solution:
K
Mm Fe = 55.85 g.mol-1
Write a balanced chemical equation for the reaction:

Fe (s) + 2HCl (aq)  FeCl2 (s) + H2 (g)

Consider case a):

The vessel is closed: therefore, no expansion work is possible, and the volume
does not change. This means DV  0
and consequently,
w 0
 The first law

Consider case b):

Since the beaker is open, the gas produced in the reaction expands against
constant pressure of the atmosphere. We use equation:
w   PDV
Consider that the initial volume of the reactants is negligible in comparison with the
volume of the gas formed. Therefore, we can write;
DV  VH 2
Where VH2 is the volume of hydrogen gas formed in the reaction.
The expression for the work done becomes;

w   P VH 2
Assume that hydrogen is an ideal gas, and write the state equation for it

P VH 2  nH 2 RT
 The first law

By comparing the last two equations, we can write;

w  nH 2 RT
Find number of moles of hydrogen gas;

50.00 g
nFe  1
 0.90mol
55.85 g.mol

From the balanced equation, n Fe = nH2, therefore;

nH 2  0.90mol

Calculate the work done:

w  nH 2 RT
w  0.90mol  8.314 J .K 1mol 1  298 K
w  2.22  103 J