CYL110

Elements of Physical Chemistry

Chemical Thermodynamics

Chemical Dynamics

Quantum Chemistry
CHEMICAL THERMODYNAMICS
A. Ramanan

QUANTUM CHEMISTRY
Dr. Sidhdharth Pandey

A. RAMANAN
MS729
aramanan@chemistry.iit.ac.in
Thermodynamics is the only science about
which I am firmly convinced that, within the
framework of the applicability of its basic
principles, it will never be overthrown.

Albert Einstein
 LECTURE 1

Properties of Gases
CO2

CaCO3(s)  Ca2+(aq) + CO32-(aq)

CO2(aq) + H2O(l)  H2CO3(aq)
H2CO3(aq) + CO32-(aq)  2HCO3-

Ca2+(aq) + 2HCO3-  CO2(aq) +

H2O(l) + CaCO3(s)
Power generation percent of different energy

A. Ramanan
Department of Chemistry
Global
Globalcarbon
carbondioxide
dioxidegeneration
generationby
bymineral
mineralfuel
fuel
(from
(fromScientific
ScientificAmerican
American2002)
2002)
Exhaust Exhaust amount of
percent(wt%) per person (ton)
America 24 5．4
China 14 0．7
Russia 6 2．7
Japan 5 2．5
India 5 0．3
Germany 4 2．8
Canada 2 4．2
Britain 2 2．5
Korea 2 2．2
Italy 2 2．0
France 2 1．7
Mexico 2 1．1
 Hydrogen

Henry Cavendish. 1731-1810. British chemist and physicist

who discovered the properties of hydrogen and established
that water is a compound of hydrogen and oxygen.

Cavendish called hydrogen “flammable air”.

The name “Hydrogen” was given by :

Antoine Laurent Lavoisier (1743-1794), French

chemist, who disproved the phlogiston theory by
determining the role of oxygen in combustion, and
organized the classification of compounds.
 Volumetric and gravimetric hydrogen density
of some selected hydrides.

Three options exist for storing hydrogen: as a highly compressed gas,

a cryogenic liquid, or in aA.solid matrix.
Ramanan
Department of Chemistry
James A. Ritter Materials today, September 2003, 24
 15 MPa compressed hydrogen gas cylinder

The hydrogen storage capacity is only 1.2 mass%.

 35 and 70MPa compressed
hydrogen gas cylinders

100 MPa compressed H2

cylinder is also being
developed.

Dangerous!

The hydrogen storage is about 2.7% at 35 MPa and 5.5 mass% at 70 MPa.
 Hydrogen storage in liquid state

Hydrogen storage in liquid state has high storage

capacity, but it resumes a lot of energy in liquefation
and low temperature keeping, therefore, the energy
utilization efficiency is low.
Volume for storage of 4 kg H2 in different states

Solid material
 H2(g) + ½ O2(g)  H2O(l)

H2(g) and O2(g) mixes violently

when initiated liberating heat
~240kJ/mol

E ~ 2.3 eV
 C (solid)

graphite

diamond

C60
Thermodynamics is the branch of
science that predicts whether a state of
some macroscopic system will remain
unchanged or will spontaneously evolve to
a new state.

Kinetics is the branch of science that

deals with how long it takes for a system
to reach that new state.
 Spontaneous Processes
• A process that is spontaneous in one direction is not
spontaneous in the opposite direction.
• The direction of a spontaneous process can depend
on temperature:

Ice turning to water is spontaneous at T > 0°C

Water turning to ice is spontaneous at T < 0°C

 Reversible Processes

• A reversible process is one that can go back and forth

between states under exactly the same conditions (the
definition of equilibrium!).

– When 1 mol of water is frozen at 1 atm at 0°C to form

1 mol of ice, q = ΔHfus of heat is removed.
– To reverse the process, q = ΔHfus must be added to
the 1 mol of ice at 0°C and 1 atm to form 1 mol of
water at 0°C.
– Therefore, converting between 1 mol of ice and 1 mol
of water at 0°C is a reversible process.

• Chemical systems in equilibrium are reversible.

 Irreversible Processes

• When 1 mol of ice melts spontaneously in a

warm room, it is an irreversible process;
water does not freeze in a warm room!

• In any spontaneous process, the path

between reactants and products is
irreversible.
 Spontaneous Processes

Thermodynamics predicts the direction of a

spontaneous process; it cannot predict the speed at
which the process will occur.

Most spontaneous processes are exothermic; they

"roll down the enthalpy hill".

But some spontaneous processes are not

exothermic; WHY?
–Thermodynamics is most relevant to the
understanding of processes on spatial scales large
enough to neglect individual atoms and
timescales long enough to neglect kinetics, so
that the predictions of thermodynamics describe
to good approximation the actual state of nature,
rather than the expected state at infinite time.
–All kinetic processes go faster with increasing
temperature, and hence the tools of
thermodynamics are most useful
– But even for kinetically limited things (like
life), thermodynamics tells which way it is
favorable for processes to run.