THERMODYNAMICS

SPECIFIC LEARNING OBJECTIVE

At the end of the session the student should be
able to explain:
Energy
The first law of thermodynamics
Entropy
Free energy

Thermodynamic

In Chemistry
System

In Living
System

THERMODYNAMICS

Thermodynamic is the law that

formulated from observation on
conversion of energy from one form
to the other. i.e. transduction

What is the energy?

1. Energy is a much used term, but it
represents a rather abstract concept.
2. Energy is usually defined as the
capacity to do work.
3. Chemist define work as directed
energy change resulting from a
process

The type of Energy

1. Kinetic energy
2. Radiant energy
3. Thermal energy
4. Chemical energy
5. Potential energy

Definition of type energy

1. Kinetic energy the energy
produced by a moving object
2. Radiant energy : comes from the
sun (solar energy) and is Earths
primary energy source. Solar energy
heats the atmosphere and Earths
surface, stimulates the growth of
vegetation through the process
known as photosynthesis, and
influences global climate patterns.
continued

The Activated Complex form the reaction:

A+B
AB#
P

Definition of type energy

3.Thermal energy is the energy

associated with the random motion of
atoms and molecules.
4. Chemical energy is stored within
the structural units of chemical
substances; its quantity is determined
by the type and arrangement of atoms
in the substance being considered.
5. Potential energy is energy that is also
available by virtue of an objects
position.

Conclusion of Energy
All forms of energy can be
interconverted (at least in principle)
from one form to another

Scientists have concluded that energy

can be neither destroyed nor created.

Thermodynamic Law

THERMODYNAMICS
Thermodynamic I is the law
of conservation of energy

Thermodynamic I

Thermodynamic II
Thermodynamic III

Work

Heat

Work and heat are

not state functions

 The relationship between chemical energy

and other forms of energy, with examples.

Energy change in chemical reactions

Almost all chemical reactions absorb
or produce (release) energy, generally
In the form of heat.
Heat is the transfer of thermal energy
between two bodies that are at different
temperatures.
Although Heat itself implies the
transfer of energy, we customarily talk of
heat absorbed or heat released when
describing the energy changes that occur
during a process.

Energy changes associated with

chemical reactions

System

Surroundings

SYSTEM AND SURROUNDING

System we mean that the part of
the world we are investigating.

Three type of systems

be
Open

Close

Isolated

Surrounding we
mean everything
else
Surrounding

system

System be open
Two of this examples are the
examples of open system:
1.e.g. in the living organism, which
takes up nutrients, releases the waste
products, and generates work and
heat.
2.An example in body, the body takes
up nutrient, and then release urine
which contains toxin, carbon dioxide,
and so on.

System be closed
Example of close system:
An example of close system is living
of an microorganism, it was sealed
inside a perfectly insulated box, it
will, together with the box, constitute
a closed system.

HEAT
q, to be the manner of energy transfer that
results from a temperature difference
between the system and its surrounding
Positive and negative
sign of heat

Heat input to a
system is
considered a
positive quantity

Heat evolved by a
system is
considered a
negative quantity.

WORK
w, to be the transfer of energy between the
system of interest and its surroundings as
a result of existence of unbalanced forces
between two.

Positive and negative sign of work

If the energy of the system is
increased by the work, we say
that work is done on the
system by surroundings, and
we take it to be a positive
quantity

if the energy of the system is

decreased by the work, or the
system does work on the
surroundings, or that work is
done by the system, and we
take it to be a negative
quantity

 The effect of work is equivalent to the

raising or lowering of mass in the
surroundings.

Work is done by the system because

the mass is raised

work is done on the system because

the mass is lowered.

ENERG
Y
Energy is a state function
It is a property that depends only upon the
state of the system, and not upon how the
system was brought to that state, or upon
the history of the system.

Thermodynamic I study
of conservation of energy

The first law of thermodynamic

U = q + w
which is essentially a statement of the
law of conservation of energy.

Where :
1. The term U represents the change of internal
energy of the system,
2. q is the thermal energy (heat) added to the
system, and w is the work done on the
system.

The chemical reactions that need energy

1. The Photoelectric Effect this is mystery
in physics.
Experiments had already demonstrated
that electrons were ejected from the
surface of certain metals exposed to light
of at least a certain minimum frequency.
Einstein suggested that a beam of light is a
stream of particles. These particles of light
are called photons. Using Plancks
quantum theory of radiation as a starting
point, Einstein deduced that each photon
must possess energy E, given by the
equation :
E = hv
In which v is the frequentcy of light and h is
Plancks constant

The equation of E = hv
E = hv
E = KE + BE hv = KE + BE
in which :
* KE is the kinetic energy of the
ejected electron and
* BE is the binding energy of the
electron in the metal

The energies that the electron

in the hydrogen atom

En = R H

1
n2

In which RH, the Rydberg constant,

has the value 2.18 x 10-18 J
The number n is an integer called the
principal quantum number; it has the
value n = 1, 2, 3,.

Strength of Covalent
Bond
The Strength of Covalent Bond is
defined by the amount of energy
needed to break it.
A quantitative measure of stability of
a molecule is its bond dissociation
energy (or bond energy).
For example:
H2(g) H(g) + H(g)
H = 436.4 kJ
HCl(g) H9g) + Cl(g) H = 431.9 kJ

Covalent Bond in Organic Compounds

STRUCTURE
SATURATED:
Bonding : are
formed by overlap
of two atomic
orbitals, each of
which contains one
electron

UNSATURATED :
and bonding.
bonding

(pi) bond

ENTHALPY
The enthalpy of a system, which has the
symbol H, is that of Heat content (heat of
reaction) and is measure of the change
in total bonding energy during a
reaction. It is defined mathematically as :
H = U + PV; H is a function of state

The standard enthalpy change for any

reaction (H0rxn)can determine by
using standard enthalpies of
formation (H0f) and Hesss Law

CONSTANT PRESSURE PROCESSES

Most processes occur in the open
at one atmosphere pressure.
In these cases, P1 = P2 = P, say,
and

H = U + P V

Positive and negative sign of Enthalpy

H has a negative sign for an
exothermic change (heat is
released), is mean the bonds in the
products are stronger (more stable)
than the bonds in the reactants.
H has a positive sign for an
endothermic change (heat is
absorbed), is mean the bonds in the
products are weaker (less stable)
than the bonds in the reactants.

HESSS LAW
The principle of constant heat
summation, often known as Hesss
Law, is thus seen to lead directly from
the fact that H is a function of state.
Hesss Law be valid for : r H or f H,
= all reactants and products are in
their standard states.
f = formation standard enthalpies of
formation
P = 1 atmosphere, and temperature
25C or 298.15K

This idea is immensely

powerful, because it enables
H298 values to be determined
for any reaction, as long as the
H of formation are known for
each reactant and product.

r H = H prod H react

Example No. 1 :
Consider the following two chemical
equations.
1. C(s) + O2 (g)
CO (g)
r H (1) = -110.5 kJ
2. CO (g) + O2 (g)
CO2 (g)
r H (2) = -283.0 kJ
How many Joule r H (3) = .? For below
equation
C (s) + O2 (g)
CO2 (g)
r H (3) = ...?

Example No. 2 :
2 P(s) + 3 Cl2(g)
2 P(s) + 5 Cl2(g)

2 PCl3(l) rH (1)= -640 kJ

2 PCl5(s) rH (2)= -887 kJ

Please calculate the value of r H for below

equation
PCl3(l) + Cl2(g)
PCl5(s) r H (3) = .....?
Please you make the application of Hesss
Law, consider the use of

solution No. 2:
2 P(s) + 3 Cl2(g)
2 P(s) + 5 Cl2(g)

2 PCl3(l) rH (1)= -640 kJ

2 PCl5(s) rH (2)= -887 kJ

Please calculate the value of r H for below

equation
PCl3(l) + Cl2(g)
PCl5(s) r H (3) = .....?
Please you make the application of Hesss
Law, consider the use of
A. 247 kJ
B. + 247 kJ

C. 124 kJ
D. + 124 kJ

E. 1527 kJ.

Spontaneous Changes
The process tends to occur or not
Two driving forces in nature
2. The tendency
1. The towards
for entropy to
minimization of energy
increase is
is one such directing
influence, but there is
natures
also a tendency for
second driving
material to become
force.
more physically
disorganized.

ENTROPY
The symbol of entropy = S
a thermodynamic function of state

NATURAL OR IRREVERSIBLE PROCESS

The entropy of system and surroundings
together increases during all natural or
irreversible process;
Ssystem + Ssurrounding = Suniverse > 0

REVERSIBLE PROCESS

For reversible process, the

total entropy is unchanged;
Ssys + Ssur = Suniverse = 0

CYCLIC PROCESSES
For a cyclic process, a process in
which the
final state is the same as the initial
state,
S = 0

Changes of entropy
with temperature

S = S2 S1 = CP ln T2/T1 (P
constant)
S = S2 S1 = CV ln T2/T1 (V
constant)

Absolute entropy

The third Law of Thermodynamics

All truly perfect crystals at absolute
zero temperature have zero entropy.

FREE ENERGY

Gibbs Free Energy

The Gibbs energy determines the
direction of a Spontaneous
Process for a System at Constant
Pressure and Temperature

G is function of state
Gibbs free energy, G,. It is a function
of state which provides possible or
not a change of any kind will tend to
occur.

The value of G
For a favorable reaction, G has a
negative value, meaning that
energy is released to the
surroundings Exergonic
For a unfavorable reaction, G has
a positive value, meaning that
energy is absorbed from the
surroundings Endergonic

REACTION AT CONSTANT
TEMPERATURE & PRESSURE

dG 0 (constant T and P)
The quantity G is called the Gibbs energy

Value of G in a system
at constant T and P

The Gibbs energy will decrease as

the result of any spontaneous
processes until the system reaches
equilibrium, where d G = 0.

 The Gibbs free energy is

defined as:
G = H - TS

RELATIONSHIP BETWEEN THE PROCESSES

WITH GIBBS FREE ENERGY

Spontaneous processes, that is, those with

negative G values, are said to be
exergonic; they can be utilized to do work.
Processes that are not spontaneous, those
with positive G values, are termed
endogonic; they must be driven by the input
of free energy.
Processes at equilibrium, those in which the
forward and backward reactions are exactly
balance, are characterized by G = 0.

Thermodynamic

In Chemistry
System

In Living
System

What was The Thermodynamic

Studied in Living System?

Thermodynamic In Living System

1. H (heat)
2. S (the extent of disorder of the
system)
3. G (Gibbs change in free energy that
proportion of the total energy change
in a system, that is available for doing
work)

Thermodynamic In Living System

Under the conditions of biochemical

reactions,
1. H (heat) is approximately equal

to E, the total change in internal

energy of the reaction,

G = H T S, become:

G = E T S

What is the difference between chemical

reaction in nonbiologic systems and in
biologic systems?
Nonbiologic systems may utilize heat
energy to perform work, but biologic
systems are essentially isothermic and
use chemical energy to power living
processes.

ATP (Adenosine Triphosphate):

The Primary Energy Carrier)
Certain bonds in ATP save the energy
released during the oxidation of
carbohydrates, lipids, and proteins.
The ATP molecules act as energy
carries, and deliver the energy to the
parts of the cell where energy is
needed to power muscle contraction,
biosynthesis, and other cellular work.

Energy source in the body

ATP plays a central
role in the
transference of free
energy from the
exergonic to the
Endergonic
processes.
It serves as a carrier
of chemical energy
between high energy
phosphate donors
and low energy
phosphate acceptors

Structure of ATP

Energy source in the body

ATP consists of
adenine (a purine),
ribose and three
phosphate groups,
out of which the
two terminal
phosphate groups
being anhydride
bonds are the high
energy groups

Structure of ATP

Energy change in chemical reactions

Almost all chemical reactions
absorb or produce (release)
Energy.
The standard free energy, i.e.
G0 of hydrolysis of ATP
1. ATP + H20 ADP + Pi
G0 = -7.3 kcal/mol
used for doing work
2. ATP + H20 AMP + PPi
G0 = -7.7 kcal/mol

Chemical reaction can use up,

or produce useful energy.
Exergonic reactions produce an energy
output (G = - means that the process is
not favorable)
Endergonic reactions require an energy
Input (G = + the criterion for a favorable
process in a nonisolated system, at
constant temperature and pressure)
Biochemical system couple these energy
yielding (exergonic: unstable to stable)
with energy requiring (endergonic: stable
to unstable) to make cellular metabolism
work.

Energy transfer in the body

The working cell
The chemical reactions within cells
are accompanied by changes in
energy.
Cells accomplish their tasks by
coupling energy-requiring reactions
with energy-producing reactions

Protein + ATP Pro-phosphate complex

+ ADP (protein is phosphorylated)

What is the reaction called, if a

reaction between solute and solvent
needs heat?

A. exergonic reaction
B. endergonic reaction
C. exothermic reaction
D. endothermic reaction
E. kinetic reaction

 The reaction of glucose become to glucose-6phosphate as follows:

Pi + glucose
glucose-6-P + H2O

G0 = +13.8 (kJ.mol-1)

ATP + H2O
ADP + Pi

G0 = -30.5 (kJ.mol-1)
ATP + glucose
ADP + glucose-6-P

G0 = -16.7 (kJ.mol-1)

What is the reaction above called?

A. exergonic reaction
B. endergonic reaction
C. exothermic reaction
D. endothermic reaction
E. kinetic reaction

Energy transfer in the body

Phosphoryl-transfer Reactions
R1-O-PO32- + R2-OH
R1-OH + R2-O-PO32 Are of enormous metabolic significance.
Some of the most important reactions of
this type involve the synthesis and
hydrolysis of ATP:

ATP + H2O
ADP + Pi

ATP + H2O
AMP + PPi
For examples: next slide

Continuation: Energy transfer in the body

The metabolism of glucose is its

conversion to glucose-6-phosphate :
Endergonic half-reaction 1:
Pi + glucose
glucose-6-P + H 2O
G0 = +13.8 (kJ.mol-1)
Exergonic half reaction 2:
ATP + H2O
ADP + Pi

G0 = - 30.5 (kJ.mol-1)
ATP + glucose
ADP +glucose-6-P
G0 = -16.7 (kJ.mol-1) Exergonic

Active transport: An energy-requiring

process involving the movement of
substances across a membrane

High muscle activity:

1. relaxed muscle + ATP

Contracted muscle +
ADP + Pi
2. ADP + phosphocreatinine
ATP + creatine

Low muscle activity:

1. Catabolic energy + ADP +Pi

ATP
2. ATP + Creatine
ADP + Phosphocreatine

THERMODYNAMICS OF LIVE
1. Living organism are open system and
therefore can never be at equilibrium.
2. The free energy from this process is
used to do work and to produce the high
degree of organization characteristic of
life.
3. Living system must maintain a
nonequilibrium state for several reasons.
For example: the ATP-generating
consumption of glucose.

Alterations in Body Temperature

FEVER AND HYPERTHERMIA:
Fever:
Is an elevation of body temperature
above the normal circadian range as
the result of a change in the
thermoregulatory center located in the
anterior hypothalamus.
A normal body temperature is ordinarily
maintained, despite environmental
variations, through the ability of the
thermoregulatory center to balance
heat oproduction by tissues (notably,
muscles and the liver) with heat
dissipation.

Continuation:
With fever, the balance is shifted to
increase the core temperature.
Hyperthermia:
Is an elevation of body temperature above
the hypothalamic set point due to
insufficient heat dissipation (e.g. in
association with exercise perspirationinhibiting drugs, or a hot environment)
the topic in Lab activity (salicylat
poisoning)

Summary References:
1. Warn, J.R.W., 1999, Concise Chemical
Thermodynamics, Second Edition,
Stanley Thornes Ltd., United Kingdom.
2. McQuarrie, D.A., Simon, J.D., 1997,
Physical Chemistry a Molecular
Approach, University Science Books,
Sausalito.