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CYL110CYL110 - Physical Chemistry: Concepts and Applications [4
cr. (3-1-0)]
Semester I 2009-2010, M, Th (9:30- 11), M-F 2:00-3:00
(MS418)
Instructors: Dr. Shashank Deep (SD) and Dr. Pramit K
Chowdhury(PKC)
Course Coordinator: Dr. Pramit K Chowdhury (PKC)
Office: MS731 (SD)Phone: 6596 (SD) E-mail:
[email protected] (SD)
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CYL 110 GradingGrading based on:Minor Tests I20% Minor Tests
II20% 2 Quizzes20% Major Test40% Passing grade is 30%.
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Recommended booksBooks and Reference Material:(i) Physical
Chemistry by Atkins and de Paula
(ii) The Elements of Physical Chemistry by Atkins
(iii) Physical Chemistry by Silbey and Alberty
(iv) Physical Chemistry by Levine
(vi) Physical Chemistry: A Molecular Approach by McQuarrie and
Simon
(vii) Physical Chemistry by Laidler, Meiser, and Sanctuary
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Course contents (chemical Thermodynamics)Zeroth law of
themodynamics, Ideal and real gases, van der Waals and virial
equations of state, Critical point.
First law of thermodynamics and internal energy, Exact and
inexact differentials, Isothermal and adiabatic processes,
Enthalpy, Joule-Thompson expansion, Heat Capacities.
Second law of thermodynamics and entropy, entropy changes in
reversible and irreversible processes.
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Course contents (Chemical Thermodynamics)Combined first and
second law, thermodynamic potentials, free energy and work, effect
of temperature and pressure on free energy.
Chemical potential, equilibrium and free energy, phase
equilibria: phase rule, phase equilibrium of one-component system,
clapeyron equation, clausius clapeyron equation, colligative
properties.
Gaseous equilibrium, Le Chateliers principle, vant Hoff
equation.
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CYL110 Tutorialshttp://web.iitd.ac.in/~sdeep
MenuCoursesCYL110
Tutorial I-V
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ThermodynamicsEffects of gravitational field, centrifugal field
and surface area on the properties of the system.
Phase transitions like graphite to diamond conversion, helium
normal to superfluid transition, conductor to semiconductor
transition, change of boiling point of a liquid with pressure or
addition of solute.
Biochemistry-Enzymes and protein stability, DNA stability,
metabolic processes leading to mechanical work performed by a
living organism, design of drugs.
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Thermo----------Industrial Chemistry-Different chemical
processes like synthesis of ammonia from nitrogen and hydrogen.
Thermodynamics of complexation with macrocyclic ligands- A
system of interest in Inorganic chemistry and chemical
separation.
Geological problems- solubility of calcite, energetics of
ternary oxides of minerological significance.
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A thermodynamic system is that portion of the Universe that we
have selected for investigationThe surroundings are everything
outside the system.
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The boundary separates the system from the surroundings
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When a system is at equilibrium, its state is defined entirely
by the state variables, and not by the history of the system. The
properties of the system can be described by an equation of state
which specifies the relationship between these variables. The state
of a system is defined as the complete set of all its properties
which can change during various specified processes.
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System--------------------------
GASVariables---------------------- n, P,V,TEquation of State
-------- PV=nRTA perfect gas is defined as A gas where
intermolecular forces are negligible.
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TemperatureZeroth law of thermodynamics.
Do we need definition of temperature ?
On a cold winters day a metal railing feels much colder than a
wooden fence post, but they are both at the same temperature.
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The zeroth law states If two systems are separately in thermal
equilibrium with a third, then they must also be in thermal
equilibrium with each other.
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Bulk VariablesV, the Volume the sample occupies (m3)m3 = 106 cc
= 1000 Lp, the Pressure of the sample (atm)1 atm = 101.325 kPa =
1.01 bar = 760 TorrT, the Temperature of the sample (K)n,
Composition - moles
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Ideal Gas ModelMolecules may be treated as point masses relative
to the volume of the system.Molecular collisions are elastic, i.e.
kinetic energy is conserved.Intermolecular forces of attraction and
repulsion have negligible effect on the molecular motion.
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CompressibilityThe compressibility of a gas is defined by If the
gas behaves ideally, then Z=1 at all pressures and temperatures.Z
>1 molecules occupy more volume than IG (e.g. H2): repulsive
forces Z < 1 molecules occupy less volume than IG (e.g. CO2):
attractive forces
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Critical constants of some gases
The very low critical pressure and temperature of helium,
reflecting the very small intermolecular attractions of this atom.
Tc of the noble gas elements increases with atomic number.
Hydrogen gas cannot be liquified above 33 K; this poses a major
difficulty in the use of hydrogen as an automotive fuel; storage as
a high-pressure gas requires heavy steel containers which add
greatly to its effective weight-per-joule of energy storage.
The properties of carbon dioxide (particularly its use as a
supercritical fluid).
The high Tc of H2O is another manifestation of its "anomalous"
properties relating to hydrogen-bonding.
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Calculation of critical pointa point on a curve at which the
tangent crosses the curve itself. a point on a curve at which the
curvature changes sign. A point on a curve at which the second
derivative changes sign. a point (x,y) on a function, f(x), at
which the first derivative, f'(x), is at an extremum, i.e. a
minimum or maximum.
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It possesses the flow properties of a gas and the solvent
properties of a liquid.
Supercritical Fluid is an example of gas which can dissolve
solids.
The density of a supercritical fluid can be changed over a wide
range by adjusting the pressure; this, in turn, changes its
solubility, which can thus be optimized for a particular
application.
Super critical fluid (Gases above their TC and Pc)
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Soluble components are extracted from a substrate by a high
pressure gas, and the extracted components that have been dissolved
in the gas are precipitated from the gas when the pressure is
reduced.
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Major drawback in using liquids as a solvent is the presence of
residual solvents in the product.Super critical fluids are used for
decaffeinating coffee and tea and extracting flavors, aroma and
essential oils from hops, spices, flowers and herbs.
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Virial equation of state
It is based on statistical mechanical theory, where each power
level indicates a higher level of interaction.
The virial equation does not tend to be very good at high
densities (low T, high P).
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Boyles temperature
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van der Waals Equationrepulsionattraction
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van der Waals constants
a (dm6 atm mole-1)
b (dm mole-1)
He
0.034
0.0237
Ar
1.345
0.0322
N2
1.390
0.0391
O2
1.360
0.0318
CO2
3.592
0.0427