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Why thermodynamics are important in

Thermodynamics is concerned with the quantitative

relationships between heat and other forms of energy. including
mechanical, chemical, electric, and radiant energy
Describing energy-related changes in reaction
Determining the fate of simple chemical processes to describing
the very complex behavior of biologic cells

Voltage source

Energy can be considered as the product of

an intensity factor and a capacity factor.
Stated more explicitly, the various types of energy may be
represented as a product of an intensive property independent
of the quantity of material, and the differential of an extensive
property that is proportional to the mass of the system.

Mechanical Energy
A body is said to possess kinetic energy because of its motion or
the motion of its parts (i.e., its molecules, atoms, and electrons),
and to possess potential energy by virtue of its position or the
configuration of its parts.
It is not possible to know the absolute value of the energy of a
system; it is sufficient to record the changes in energy that occur
when a system undergoes some transformation.

Basic Definitions of Thermodynamics

A system is a well-defined part of the universe

The system is separated from surroundings, by physical or virtual
Work is a transfer of energy that can be used to change the height
of a weight somewhere in the surroundings
Heat is a transfer of energy resulting from a temperature difference
between the system and the surroundings
Both work and heat only appear at the systems boundaries where
the energy is being transferred

The First Law of Thermodynamics

The first law is a statement of the conservation of
energy. It states that, although energy can be
transformed from one kind into another, it cannot be
created or destroyed.
The total energy of a system and its immediate
surroundings (which together are often referred to as
an isolated system) remains constant during any

The First Law

A close system is one that may
exchange heat and work but not
matter with its surroundings

An open system involved a transfer

of matter in addition to the
exchange of heat and work

The First Law of Thermodynamics

According to the first law, the change in internal energy (E) is
related to heat (Q) and work (W) transferred between the
system and its surroundings
E = E2 + E1 = Q + W
E2 = internal energy of the system in its final state
E1 = internal energy of the system in its initial state of the atoms, ions, or
molecules of

The internal energy is related to the microscopic motion of

which the system is composed

The First Law of Thermodynamics

By using E = E2 + E1 = Q + W equation, the change of internal
energy can be evaluated by measuring Q and W during the
change of state.
Infinitesimal change in the energy dE is written
dE = dq + dw
Where dq is the heat absorbed and dw is the work done during infinitesimal
change of the system

The First Law of Thermodynamics

Isothermal and adiabatic processes

When the temperature is kept constant during a process, the
reaction is said to be conducted isothermally
When heat is neither loss or gained during a process, the
reaction is said to occur adiabatically
In adiabatic process dq = 0 therefore,
dw = dE
When work is done by the system, the internal energy decreases, and
because heat cannot be absorbed in adiabatic process, the temperature must
The work dependent only on the initial and final states of the system.

The First Law of Thermodynamics

A vapor confined in a hypothetic cylinder fitted with
a weightless, frictionless piston of area A. If a
constant external pressure P is exerted to the piston,
the total force is P x A. The vapor in the cylinder is
now made to expand by increasing the temperature,
and the piston moves to the distance h. The work
done against the opposing pressure is
A x h is the increase in volume V = V2 V1
Therefore at constant pressure
W = P V

The First Law of Thermodynamics

Reversible processes
A process which is always in a state of virtual thermodynamic
equilibrium, being reversed by an infinitesimal change of
pressure, it is said to be reversible.

If the pressure on the system is increased or decreased rapidly, or

if the temperature of the bath cannot adjust instantaneously to
the change in the system, the isolated system is not in the same
thermodynamic state at each moment, and the process is

Exercise : Application of the first law of thermodynamics

The First Law of Thermodynamics

Maximum work
The work done by a system in an isothermal process
is at a maximum when it is done reversibly.
What is the maximum work done in
the isothermal reversible expansion of
1 mole of an ideal gas from 1 to 1.5
liters at 25C?
Wmax = - n RT ln (V2/V1)

Ideal gas equation

PV = nRT
R is the gas constant
8.31451 J K-1 mol-1
1.98722 cal K-1 mol-1

Many chemical and physical processes are carried out at atmospheric (essentially
constant) pressure. Under this condition the work of expansion is done at constant
pressure, the heat exchanged equals to the change in enthalpy.
W = - P V = - P (V2 - V1)
E = Q + W
E = Qp - P (V2 - V1)
Qp is the heat absorbed at a constant pressure
Qp = E2 - E1 + P (V2 - V1)
Qp = E2 + PV2 - E1 + PV1 Qp = H (negative = exothermic, positive = endothermic)

enthalpy H
The increase in enthalpy H is equal to the heat absorbed at constant pressure
The change in enthalpy accompanying a chemical reaction remains a function only
of temperature.

The formation of methane:
C(s) + 2H2(g) == CH4(g)
The combustion of methane:
CH4(g) + 2O2(g) == CO2(g) + 2H2O(l)

Hcomb(25C) = -212.8 kcal

CO2(g) + 2H2O(l) == CH4(g) + 2O2(g)

Hcomb(25C) = +212.8 kcal

C(s) + O2(g) == CO2(g)

Hf(25C) = -94.052 kcal

2(H2(g) + 1/2O2(g) == H2O(l))

2 (Hf(25C) = -68.317 kcal)
C(s) + 2H2(g) == CH4(g)

Hf(25C) CH4(g) = -Hcomb + Hf CO2(g) + 2 x Hf (H2O(l))

= 212.8 kcal + (-94.052 kcal) + 2(-68.317 kcal) = -17.886 kcal

Exercise: Thermochemistry
If breaking C=C bond requiring 130 kcal, breaking Cl-Cl bond requiring 57 kcal,
formation of C-C bond liberating 80 kcal and formation of C-Cl liberating 78
kcal of energy. What is the enthalpy change H of the reaction of ethene and
chlorine into dichlorethane?
1 cal = 4.184 joules

The Second Law of Thermodynamics

o The first law of thermodynamics observed that energy must
be conserved when it is converted from one to another not
about the probability that a process will occur.
o The second law refers to the probability of the occurrence of a
process based of the observed tendency of a system to
approach a state of energy equilibrium
o Heat flows spontaneously only from hotter to colder bodies,
and a steam engine can do work only with a fall in
temperature and a flow of heat to the lower temperature.
o No useful work can be obtained from heat at constant

The Second Law of Thermodynamics

o Gases expand naturally from higher to lower pressures,
and solute molecules diffuse from a region of higher to
lower concentration.
o These spontaneous processes will not proceed in reverse
without the intervention of some external agency.
o Although spontaneous processes are not
thermodynamically reversible (irreversible), they can be
carried out in a nearly reversible manner by an outside

The Second Law of Thermodynamics

o The energy that may be freed for useful work in a gas,
liquid, or solid, or any reaction mixture, is known as the
free energy of the system.
o The free energy decreases as a physical or chemical
reaction proceeds.
o In general, spontaneous processes at constant
temperature and pressure are accompanied by a loss in
free energy, and this decrease signifies the natural
tendency for the transformation to occur.

The Second Law of Thermodynamics

o An important consideration is that of the possibility of
converting heat into work.

o Not only is heat isothermally unavailable for work; it

can never be converted completely into work.
o The spontaneous character of natural processes and
the limitations on the conversion of heat into work
constitute the second law of thermodynamics.

The Second Law of Thermodynamics

The efficiency of the heat engine

The Second Law of Thermodynamics

The efficiency of the heat engine

Exercise: The second law of thermodynamics

What is the entropy change S accompanying the vaporization of 1 mole of
water in equilibrium with its vapor at 25C. This is a reversible and isothermal
process and carried out at a constant pressure. The heat of vaporization Hv
required to convert the liquid to the vapor state is 10,500 cal/mole.

The Third Law of Thermodynamics

o The third law of thermodynamics states that the
entropy of a pure crystalline substance is zero at
absolute zero because the crystal arrangement
must show the greatest orderliness at this

o The third law cannot be applied to supercooled

liquids because their entropy at 0 K is probably not

H and S for the transition from liquid water to ice at -10C and at 1 atm
pressure are 1343 cal/mole and -4.91 cal/mole deg, respectively. What is
the G for the phase change at this temperature and indicate whether this
process is spontaneous?

The Third Law of Thermodynamics

o Two new thermodynamic properties, the Gibbs free energy G and
the Helmholtz free energy or work function A are now introduced,
and some applications of these important functions to chemistry
and pharmacy are considered.
o These functions may be related to the other thermodynamic
quantities in the following way. Disregarding electric and other
forms of energy, we consider PV work as the only useful work or
external energy that a system can accomplish.

The Third Law of Thermodynamics


The heat content or total energy of the system is then divided into interna
and external energy:

H =



The total heat maybe divided into isothermally available or free energy
G and isothermally unavailable energy TS

H =



The Third Law of Thermodynamics

Finally, the internal can be divided into isothermally available internal
energy or work function A and isothermally unavailable energy TS.
Thus, for an isothermal process

E =



The Third Law of Thermodynamics

A number relationships maybe obtained by rearranging these
quantities and placing various restrictions on the processes described

G =
G =
G =

H - TS
E + PV A + PV


What is the free energy change when 1 mole of an ideal gas is compressed from 1
atm to 10 atm
Determine the change in the entropy, Helmholtz free energy, and Gibbs free
energy, when a mole of ideal gas is compressed from 1atm to 100 atm at 20C.
What is the free energy change when the kidneys transfer various chemical
constituents at body temperature from the blood plasma to the more
concentrated urine. The concentration of urea in the plasma is 0.005 mole/liter; in
the urine is 0.333 mole/liter. Calculate the free energy change in transporting 0.1
mole of urea from the plasma to the urine.

If the molar concentration of a monomeric species of Sodium cholate at 25C is
4 x 10-3 mole/liter and the concentration of dimeric species is 3.52 x 10-5
mole/liter, what is the equilibrium constant and the standard free energy for the
dimerization process?

The Laws of Thermodynamics

The First Law of Thermodynamics
Energy is conserved; it can be neither created nor destroyed

The Second Law of Thermodynamics

In an isolated system, natural processes are spontaneous when
they lead to an increase in disorder, or entropy

The Third Law of Thermodynamics

The entropy of a perfect crystal is zero when the temperature of
the crystal is equal to absolute zero