Laws of Thermodynamics

Geochemistry BS Geology
Department of Earth & Environmental Sciences,
Bahria University, Islamabad

Thermodynamics
Thermodynamics is the study of the heat, energy

and effects of work on a system

It is a theory of the relations between heat and

mechanical energy, and of the conversion of either

into the other.
Thermodynamics is only concerned with
macroscopic (large-scale) changes and
observations
Volume, Temperature, Pressure, Heat Energy, Work.

Importance in Geology
In geology, thermodynamics relates to the stability

of rocks and minerals under varying heats and

pressures.

Thermodynamics not only allows us to predict

what minerals will form at different conditions

(forward modeling), but also allows us to use
mineral assemblages and mineral compositions to
determine the conditions at which a rock formed
(thermobarometry).

Terminology

a system:
Some portion of the universe that you wish to study

The surroundings:
The adjacent part of the universe outside the system

Changes in a system are associated with the

transfer of energy

Natural systems tend to attain states of

minimum energy or equilibrium

a Phase: a mechanically separable portion of

a system

Mineral
Liquid
Vapor

a Reaction: some change in the nature or

types of phases in a system

Gibbs Free Energies of

Phases
All phases, whether mineralogical or not, have
an associatedGibbs Free Energy of
Formationvalue abbreviatedas Gf.
TheGfvalue describes the amount of energy

that is released or consumed when a phase is

created from other phases.

Gibbs Free Energy of

Reactions
TheGibbs free energy (G )tells us
rxn

whether a reaction will take place.

Grxnis the Gibbs Free Energy of the right
hand side of a reaction, minus the Gibbs Free
Energy of the left hand side.
IfGrxn< 0, the reaction will proceed to the

right; if it is > 0, the reaction will proceed to

the left.

Consider the example of Enstatite. The Gibbs Free

Energy of Formation for Enstatite (MgSiO3) from pure

elements Mg, Si and O (Gfenstatite, elements) is
about -1,460.9 J/mole at room temperature and
pressure.
The Gibbs Free Energy of Formation for enstatite from

oxides (MgO and SiO2) =Gf(enstatite, oxides) is

about -35.4 J/mole at room temperature and pressure.
Negative values indicate that enstatite is more stable
than, and will form from, the separate elements or
separate oxides at room P,T.

Enthalpy of Reaction
Theenthalpy of reaction (H rxn)tells us how

much heat will flow in or out of the system in a

chemical reaction.
IfHrxn< 0, the reaction is exothermic it releases

heat. For example, combustion of carbon based

compounds (C + O2= CO2) gives off a lot of heat.
IfHrxn> 0, the reaction isendothermic it

consumes heat. Melting ice [H2O (ice) = H2O (water)]

is endothermic.

Entropy of a Reaction
Theentropy of a reaction (S rxn)tells us

whether the products or the reactants are

more disordered.
For example, the reaction of liquid water to

steam (boiling) has a large associated entropy.

The steam molecules are more dispersed, are

less well bonded together, and have greater

kinetic energy.

Internal Energy &

Temperature
Internal energy (also called thermal energy) is
the energy an object or substance have due to
the kinetic and potential energies associated with
the random motions of all the particles that make
it up.
The hotter something is, the faster its molecules

are moving or vibrating, and the higher its

temperature. Temperature is proportional to the
average kinetic energy of the atoms or molecules
that make up a substance

Internal Energy & Heat

The term heat refers is the energy that is

transferred from one body or location due to a

difference in temperature. Heat is internal energy
when it is transferred between bodies.
Technically, a hot potato does not possess heat;

rather it possesses a good deal of internal energy

on account of the motion of its molecules. If that
potato is dropped in a bowl of cold water, we can
talk about heat: There is a heat flow (energy
transfer) from the hot potato to the cold water; the
potatos internal energy is decreased, while the
waters is increased by the same amount.

Thermal Equilibrium
Two bodies are said to be at thermal

equilibrium if they are at the same

temperature. This means there is no net
exchange of thermal energy between the two
bodies.

hot

26 C

heat cold

26 C

Types of Processes
Isobaric Processes:
Transformations at constant pressure
dp = 0

p
i

V
Isochoric Processes:
Transformations at constant volume
dV = 0

i
f
V

Types of Processes
Isothermal Processes:
Transformations at constant temperature
dT = 0

i
f
V

Adiabatic Processes:
Transformations without the exchange of heat
between the environment and the system
dQ = 0

The Zeroth Law of Thermodynamics

If object A is in thermal
equilibrium with object C,
and object B is
separately in thermal
equilibrium with object C,
then objects A and B will
be in thermal equilibrium
if they are placed in
thermal contact.

The First Law of

Thermodynamics
The first law of thermodynamics is a

statement of the conservation of energy.

Energy neither can be created nor destroyed.

If you burn a piece of wood, you change the

potential chemical energy of the wood into

thermal (heat) energy, and the wood transforms
from a log into smoke and ashes. You have altered
the wood but not destroyed it.

The First Law of Thermodynamics

If a systems volume is constant, and heat is
added, its internal energy increases.

The First Law of Thermodynamics

If a system does work on the external world, and
no heat is added, its internal energy decreases.

The First Law of Thermodynamics

Combining these gives the first law of
thermodynamics.
The change in a systems internal energy is
related to the heat Q and the work W as
follows:
It is vital to keep track of the signs of Q and
W.

The Second Law of

Thermodynamics
It states that the amount of energy doesn't

stay the same in a transfer of energy or

energy conversion.
For example, it takes a certain amount of

energy to charge a battery. But the amount of

energy that the charged battery can produce
(to power a flashlight, for example) is less
than the amount of energy needed to charge
it in the first place.

The Second Law of Thermodynamics

We observe that heat always flows
spontaneously from a warmer object to a cooler
one, although the opposite would not violate
the conservation of energy. This direction of
heat flow is one of the ways of expressing the
second law of thermodynamics:
When objects of different temperatures are
brought into thermal contact, the spontaneous
flow of heat that results is always from the high
temperature object to the low temperature
object. Spontaneous heat flow never proceeds
in the reverse direction.
2nd law is also called as Law of Increased

Entropy
It is a measure of number of specific ways in
which a system can be arranged or a measure of
a system s progression towards thermal
equilibrium.

Entropy is a state function ( have certain value

at a particular stage of system)

Entropy of a reversible system remain

conserved

The total entropy of the universe increases

whenever an irreversible process occurs.
The total entropy of the universe is unchanged
whenever a reversible process occurs.
The entropy is maximum when a system
reaches thermal equilibrium
Since all real processes are irreversible, the
entropy of the universe continually increases

Entropy
If we look at the ultimate fate of the universe
in light of the continual increase in entropy,
we might envision a future in which the entire
universe would have come to the same
temperature.
At this point, it would no longer be possible to
do any work, nor would any type of life be
possible.
This is referred to as the heat death of the
universe.

The Third Law of

Thermodynamics
Third Law of Thermodynamics states that

since heat produces motion and heat does not

exist at absolute zero. Therefore, at absolute
zero an object has neither potential energy
nor molecular disorder.

Absolute zero is a temperature that an object

can get arbitrarily close to, but never attain.

Questions????