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 In Living
System 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 Work Heat

Work and heat are

Thermodynamic II not state functions

Thermodynamic III
 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.

Surrounding we
Three type of systems mean everything
be else
Surrounding

Open Close Isolated

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 Heat evolved by a

system is system is
considered a considered a
positive quantity 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 if the energy of the system is

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

1
En = R H
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: UNSATURATED :
Bonding : are and bonding.
formed by overlap bonding
of two atomic
orbitals, each of
which contains one
electron

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

2 P(s) + 5 Cl2(g) 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 PCl3(l) rH (1)= -640 kJ

2 P(s) + 5 Cl2(g) 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 C. 124 kJ E. 1527 kJ.
B. + 247 kJ D. + 124 kJ
 Spontaneous Changes

The process tends to occur or not

Two driving forces in nature

1. The towards 2. The tendency

minimization of energy for entropy to
is one such directing increase is
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 In Living
System 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-6-
phosphate 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 perspiration-
inhibiting 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.