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Slide-02 : Inorganic Reaction

CHEMICAL ENERGY AND


THERMODYNAMICS

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Inorganic Reaction Slide 02

The 1st Law of Thermodynamics :


In ordinary processes, energy is conserved, it is
neither created nor destroyed

q
heat
SYSTE
M

W
work

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Inorganic Reaction Slide 02

If heat q is added to a system and work w is done


by the system, then the amount of energy added to
the system is (q - w)

This energy is not destroyed but is stored within the


system to increase the internal energy of the
system U.

q
heat
SYSTE
M

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Inorganic Reaction Slide 02

W
wor
k

THE INTERNAL ENERGY : The total energy

U = q - w
Unuclear

MeV

Uelectronic

: nuclear binding
energy
: electronic energy

Uvibration

: vibration energy

cal/mole

Urotation

: rotation energy

cal/mole

Utranslation : translation energy


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eV

cal/mole

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TOTAL ENERGY
= Internal Energy

Daltons Atomic Theory (1808)


1. All elements are composed of submicroscopic indivisible parts called
atoms.
2. Atoms of the same element are
identical, those of different atoms
are different.
3. Atoms of different elements
combine in whole number ratios to
form compounds.
4. Chemical reactions involve the
rearrangement of atoms. No new
atoms are created or destroyed.
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Inorganic Reaction Slide 02

Chemical Energy :
Chemical reactions involve the
rearrangement of atoms. No new
atoms are created or destroyed.
(Daltons Atomic Theory)

The energy involved in chemical


reactions is in the range of several
electron volt (1 eV = 23.06 Kcal/mole)

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Inorganic Reaction Slide 02

U = q - w

A CONCEPT
unmeasurable

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A PHYSICAL
QUANTITY
measurable

Inorganic Reaction Slide 02

A PHYSICAL
QUANTITY
measurable

U : How to measure?
Considering that mechanical work w is equal
to pV :

U = q - p V
U = q v
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measurable calorimetrically
at constant volume

Inorganic Reaction Slide 02

Since most chemical processes proceed at constant pressure


rather than at constant volume, it is more convenient to use
other new definition of internal energy called enthalpy :

H = U + pV or H = U + pV

U + p V = qp
H = q p
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measurable calorimetrically
at constant pressure

Inorganic Reaction Slide 02

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If enthalpy (or internal energy) is the driving


force of chemical processes, it is reasonable
to expect that all chemical processes should
be followed by a heat release (exothermic).

In practice, however, although it is true that


most chemical processes are exothermic,
some endothermic (heat absorbed) chemical
processes do exist.

It may be concluded, therefore, that


enthalpy (or internal energy) is NOT the
driving force of chemical processes
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The 2nd Law of Thermodynamics :

It is impossible to have chemical


processes, working with a 100 %
efficiency. Some waste energy must
also be released.

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THE CONCEPT OF FREE ENERGY

G =
Net energy

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H - TS
Total
energ
y

Inorganic Reaction Slide 02

Correction
for useless
Energy

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GIBBS FREE ENERGY

G = H - T S
Chemica
l
Bonding

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Inorganic Reaction Slide 02

System
Structurin
g

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CHEMICAL
BONDING : A

Thermodynamic Perspective

+
A

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A B

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ATRACTIVE ENERGY :
Between nucleus A and
electron B
Between electron A and
nucleus B

Uatt= - Catt/r

REPULSIVE ENERGY :
Between nucleus A and
nucleus B
Between electron A and
electron B

Urep= + Crep/r

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U
Urep= + Crep/r

r
Uatt= - Catt/r

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Urep= + Crep/r

Uatt= - Catt/r

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BOND ENERGY :
The energy required to break down
chemical bond into separate atoms

BOND LENGTH :
The equilibrium distance between two
atoms involving chemical bond.

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BOND ENERGY vs INTERAL


ENERGY
INTERNAL ENERGY U :
The most stable chemical bond would
be formed at the lowest internal
energy

BOND ENERGY :
The stronger chemical bond would be
formed with larger bond energy
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U
rAB : Bond Length
rAB

EAB

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EAB : Bond Energy

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Chemical processes tend to proceed


spontaneously in the direction of
diminished free energy, i.e. when the
free energy change, G, is negative.

G is the driving force


of chemical processes
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THE DRIVING FORCE

G = H - TS
The Degree of
Disorder of the
Structure

The Strength
of Chemical Bond
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CHEMICAL BONDS

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Electrostatic
Approach

Coulombic
Forces

CHEMICA
L
BONDING
Electron
sharing
Approach

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Sharing of
electron pair

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Electrostati
c Approach

CHEMICA
L
BONDING
Electron
Sharing
Approach
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Ionic Bond

normal

Covalent Bond
Metalic Bond

coordinatio
n

Hydrogen Bond
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BOND STRENGTH
STRONG
CHEMICAL
BONDS

WEAK
CHEMICAL
BONDS

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LARGE
BOND
ENERGY

SMALL
BOND
ENERGY

~
~

LOW
INTERNA
L
ENERGY

LOW
ENTHALP

HIGH
INTERNA
L
ENERGY

HIGH
ENTHALP

Inorganic Reaction Slide 02

ENTHALP
Y

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ENTROPY

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ENTROPY
EXPERIMENT
P, V, T

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P, V, T

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MORE ORDRED
LESS DISORDRED
LOWER ENTROPY

LESS ORDERED
MORE
DISORDERED
HIGHER
ENTROPY
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Boltzmanns Concept of
Entropy :

S = ln

The Degree of
Disorder
Entropy
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Thank You

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