Introduction to Thermodynamics

❑ Thermodynamics can be defined as the study of energy,

energy transformations and its relation to matter.
❑ The analysis of thermal systems is achieved through the
application of the governing conservation equations,
namely Conservation of Mass, Conservation of Energy
(1st law of thermodynamics), the 2nd law of
thermodynamics and the property relations.
❑ Energy can be viewed as the ability to cause changes.
The study of thermodynamics enables us to answer the very
basic question:
“What causes chemical reactions to occur?” This could be
accounted for by two reasons:

1. Energy term must be the driving force for any chemical

reaction to occur

2. Spontaneity (Self drive)

0th Law of Thermodynamics
If A is in thermal equilibrium with B, and B is in thermal
equilibrium with C, then C is also in thermal equilibrium with A.
1st Law of Thermodynamics
Energy of the universe is constant (conserved). DE = q + w
q = heat absorbed by the system, w = work done on the system
nd
2 Law of Thermodynamics
In a spontaneous process, the entropy of the universe increases.
ΔSuniverse = ΔSsys + ΔSsurr > 0 (if spontaneous)
3rd Law of Thermodynamics
The entropy of a pure crystalline substance at absolute zero is
zero: S(0 K) = 0.
Types of systems ❑ Boundary: the real or
– open (exchange of mass imaginary surface that
and energy) separates the system
– closed (exchange of from its surroundings.
energy) ❑ The boundaries of a
– isolated (no exchange) system can be fixed or
movable.
Mathematically, the
boundary has
❑ zero thickness, no
mass, and no volume.
A system is considered under thermodynamic
equilibrium when there is no more macroscopic
movement nor any kind of flux.
Thermodynamic variables are the quantities used
to characterize a system.
State functions depend Intensive -- the property is independent
only on initial and final of the size of the system (it has the same
states of the system and value for a small region of the system as
not on how the change for the whole system). e.g. temperature,
was carried out. pressure.
– Energy (E) Extensive -- the property is dependent
– Pressure (P) on the size of the system (the value
– Volume (V)
changes between a small
– Temperature (T)
Most thermodynamic quantities region of the system and the whole
(variables) are extensive state system). e.g. mass, volume, energy.
functions.
1st LAW OF THERMODYNAMICS
(The Law of Conservation of Energy)
The algebraic sum of all energy changes in an
isolated system is zero.
We define U as the internal energy of a system. From the 1st Law, U
must be a state function. Thus;
DU = U - U final initial

For an isolated system, from the 1st Law DU = 0.

For a closed system, the internal energy of the system can increase as
long as the internal energy of the surroundings decrease by the same
amount.
DU = - DU
system surroundings
Work and heat Distinction between work and heat
As we shall see, it is useful to
distinguish between two classes ❑ Work is the energy associated
of energy, work and heat. with orderly movements of
Again, we can define; bodies, for example pushing
back boundaries (volume
q - heat absorbed by the
change) or moving electrons
system from the along a wire.
surroundings ❑ Heat is the energy associated
w - work done on the with disorderly movements of
system by the surroundings bodies, for example random
DU = q + w
system
molecular motion in a gas.
Work in chemical systems
The work energy term (w) is also the sum of many different
types of energy, the most common being
▪ electrical work (such as electrochemical cells),
▪ mechanical work (such as muscle contraction) and
▪ change of volume (expansion).
w=w +welectrical +w
mechanical expansion

Most of these are usually zero. However, at constant

pressure (where life exists) the volume of the system often
changes and thus does work by pushing back the
surroundings
In this case, w is given
By w = - PDV
expansion

DV is the increase in volume of the system.

w is negative because, by increasing in volume, the system

is doing work on the surroundings.
•When a system releases
heat, some of the chemical
energy is released as thermal
energy to the surroundings
but this does not change the
total energy of the universe.
Work and heat
DUsys = q + w
∆Usystem + ∆Usurroundings = 0 where q is heat
w is work
Sign Conventions of q and w
State and Equilibrium
➢ At a given state, all the properties of a system have fixed values.
Thus, if the value of even one property changes, the state will
change to different one.
➢ In an equilibrium state, there are no unbalanced potentials (or
driving forces) within the system. A system in equilibrium
experiences no changes when it is isolated from its surroundings.
1. Thermal equilibrium: when the temperature is the same
throughout the entire system.
2. Mechanical equilibrium: when there is no change in pressure at any point
of the system. However, the pressure may vary within the system due to
gravitational effects.
3. Phase equilibrium: in a two phase system, when the mass of each
phase reaches an equilibrium level.
4. Chemical equilibrium: when the chemical composition of a system
does not change with time, i.e., no chemical reactions occur.

Processes and Cycles

❑ Any change a system undergoes from one equilibrium state to

another is called a process

❑ the series of states through which a system passes during a process

is called a path.
To specify a process, initial and final states and path must be specified
❑ Quasi‐equilibrium process: can be viewed as a sufficiently
slow process that allows the system to adjust itself internally
and remains infinitesimally close to an equilibrium state
at all times.
❑ Quasi‐equilibrium process is an idealized process and is not a
true representation of the actual process.
❑ Actual processes are modeled with quasi‐equilibrium ones.
❑ They serve as standards to which actual processes can be
compared
❑ Process diagrams are used to visualize processes.
❑ the process path indicates a series of equilibrium states, and we are
not able to specify the states for a non‐quasiequilibrium process.
Prefix iso‐ is used to designate a process for which a particular
property is constant.
Isothermal: is a process during which the temperature remains
constant
Isobaric: is a process during which the pressure remains constant
Isometric: is process during which the specific volume remains
constant.
Adiabatic process there is no exchange of heat between the system
and the surroundings.
A system is said to have undergone a cycle if it returns to its initial
state at the end of the process.
DIRECTION OF A CHEMICAL REACTION

Reactions Direction Enthalpy

Dissolution of NaNO Spontaneous Endothermic (DH = +ve)

Dissolution of NaOH Spontaneous Exothermic (DH = -ve)

Diffusion of Na+ in water Spontaneous DH = 0

❑ Thus, consideration of enthalpy (or internal energy) does not give us

any information about the direction of a chemical reaction.
❑ In fact, in any isolated system (such as the universe) DH = 0 from the
1st law, yet changes do occur in the universe.
❑ The 1st law of thermodynamics can be thought of as an accounting
tool, used to keep track of energy during a reaction.
2nd LAW OF THERMODYNAMICS
Spontaneous process occurs without external intervention
• Spontaneous changes are those which, if carried out under the
proper conditions, can be made to do work.
• If carried out reversibly they yield a maximum amount of work.
• In irreversible (spontaneous) processes the maximum work is
never achieved.
ENTROPY ,S , is a measure of the randomness of the system
We define the ENTROPY, S, of a system as:

TDS is a measure of the change in the heat energy of the system (energy
unavailable to do any further work).
Cp and Cv are heat capacities at constant pressure and heat capacities
at constant volume, respectively
For any system;
Change in total energy = Change in work energy + Change in heat
energy
DH - change in total energy (after allowing for expansion)
TDS - change in heat energy
Thus;
DH = Change in work energy + TDS
or;
Change in work energy = DH - TDS
If a change has occurred, then we must have used work energy to make
the change happen and so the change in work energy must be -ve.
Isolated system
There is no external source of energy. Only internal work energy
can be used.
DH = 0  Change in work energy = -TDS
The amount of work energy can never increase.
Thus; DS  0
If DS = 0, there is no work energy being used and so the system does not
change (equilibrium).
If DS > 0, work energy is being used and so the system can change
(Sponteneous process).
Closed systems
External energy is available.
DH  0  Change in work energy = DH-TDS
The amount of work energy can never increase during a change.
Thus DS  DH/T.
POSITION OF
EQUILIBRIUM
DG can be used to
determine how far
a reaction will go
by letting the
system change a
small amount and
then recalculating
DG.
 CONTROL OF REACTIONS
Thermodynamic control Kinetic control
• The products are in • The products are not in equilibrium with
equilibrium with the reactants. the reactants. [This does not mean that an
• The ratio of products to equilibrium cannot be established, only
reactants depends on the that is has not been established so far].
relative energies of the two • The amount of product depends on the
states (see later lectures). amount of reactant, the speed of the
• The reaction can be made to go reaction and how long it has been going.
forwards or backwards by • The reaction cannot be made to go
increasing the concentrations backwards by increasing the concentration
of the reactants or products of the products (until after equilibrium has
respectively. been established).