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Slide-02 : Inorganic Reaction

THERMODYNAMICS

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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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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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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

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eV

cal/mole

Inorganic Reaction Slide 02

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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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

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

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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
Inorganic Reaction Slide 02

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It is impossible to have chemical

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

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G =
Net energy

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H - TS
Total
energ
y

Correction
for useless
Energy

12

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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Inorganic Reaction Slide 02

A B

14

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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Inorganic Reaction Slide 02

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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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Inorganic Reaction Slide 02

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U
rAB : Bond Length
rAB

EAB

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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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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

Inorganic Reaction Slide 02

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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
Inorganic Reaction Slide 02

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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

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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Inorganic Reaction Slide 02

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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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