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Thermodynamics
Thermodynamics
Thermodynamics
Electrochemistry
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To specify a process,
initial and final states and
path must be specified.
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State function
Do not depend on the path by which the
system arrived at its present state
internal energy, entropy or enthalpy and so
on
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Path function
Depend on the path by which the system
arrived at its present state
Work done etc.
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𝑊𝑜𝑟𝑘=𝐹𝑜𝑟𝑐𝑒 ×𝐷𝑖𝑠𝑝𝑙𝑎𝑐𝑒𝑚𝑒𝑛𝑡
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Fig. 1
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Ref: Puri Sharma Pathania Physical Chemistry Book
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Fig. 1
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Convention of work:
Fig. 1
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Ref: Puri Sharma Pathania Physical Chemistry Book
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Chemical reaction
Exothermic Endothermic
Heat is liberated into the Heat is absorbed from
surroundings the surroundings
H0 H 0
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Processes in Thermodynamics:
Isothermal process: If a change takes place in such
way that temperature remains constant throughout,
is called isothermal process (dT=0).
Adiabatic process: A process is said to an adiabatic,
if no heat enters or leave the system during any step
of the process (i.e., dq=0).
Isobaric process : At constant pressure.
Isochoric process : At constant volume.
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Temperature
The concept of temperature springs from the
observation that a change in physical state can
occur when two objects are in contact with one
another as when a red-hot metal is plunged into
water.
Change in state can be interpreted as arising from
a flow of energy as heat from one object to another.
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Ref: Atkins' Physical Chemistry - Oxford University Press
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Enthalpy
The term Enthalpy (Heat content) is the total
energy content of a system by which it can do
the work.
For solids/liquids, H = U ?
For gas: 𝑼+𝑷𝑽= 𝑯, where H is enthalpy
1. It is an extensive property.
2. It is a state function.
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Heat capacity
Heat capacity of the system is define as the
quantity of the heat is required to raise the
temperature of the system from the lower to
the higher temperature divided by the
temperature difference.
𝑪=𝒅𝒒/𝒅𝑻
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Cp Cv = R
dq = dU + dW
dU = Cv dT and dq = Cp dT
Therefore CP dT = CV dT + PdV
For ideal gas PdV = nRdT
So, CP dT = CV dT + nRdT
So, (CP CV) dT = nRdT
CP CV = nR
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Thermochemistry
Thermochemistry is the study of the energy
transferred as heat during the course of chemical
reactions .
Calorimetry is used to measure the energy
supplied or discarded as heat by a reaction, and
can identify q with a change in internal energy.
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CARNOT CYCLE
Carnot's theorem, developed in 1824 also
called Carnot's rule, is a principle that specifies limits
on the maximum efficiency any heat engine can obtain
CARNOT CYCLE
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Practice at Class
1. Five mole of ideal gas expands reversibly from an initial pressure 10 atm. to a
final of 0.4 atm.; the temperature being kept constant at 0C. How much work is
done by the gas? What is the change in U and H? How much heat is absorbed?
2. For a certain ideal gas what will be the maximum work performed in the
expansion of 2 moles of the gas from 4 to 40 liters at 300 K?
4. Heat supplied to a Carnot engine is 2000 kj. How much useful work
can be done by the engine which works between 0°C and 120°C?
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Entropy
It is the measure of randomness or
disorderliness at the molecular level of the
system and denoted by S.
It is an extensive property and state
function.
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Entropy of universe
A system absorb heat from surroundings or release
heat to surroundings both system and surroundings
undergo change in entropy.
Heat change of surroundings is equal but the negative
of the heat change of the system in reversible process.
qsys = qsurr
Suniverse= Ssys+ Ssurr = 0
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To Illustrate:
Fluid always flows from higher to lower
elevation spontaneously.
Heat always flows from high to low
temperature spontaneously.
Material always diffuse from high to low
concentration spontaneously.
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Water
Ice
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Free energy
The thermodynamic functions which consider both
energy and randomness together are known as
free energy functions
1. Gibb’s Free EnergyG = H – TS
2. Helmholtz free energy F or A = U – TS
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We know, G = H - TS
Or dG = dH – TdS – SdT ………… (1)
Again, we know H = U + PV
Or, dH = dU + PdV + VdP …………… (2)
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Electrochemistry and
Electromotive force
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Daniel cell
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Electrochemical
series is a series of
chemical elements
arranged in order
of their standard
electrode
potentials.
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Solved Problems
1. Calculate E and G for the reaction, Cr2+ + 2e- Cr (s)
at 298K, Given: Cr3+ +3e- Cr (s); E = 0.50V, and Cr3+ + e-
Cr2+; E = - 0.410V.
The reactions can be arranged as
Cr3+ +3e- Cr (s); E = 0.50V
Cr2+ Cr3+ + e- ; E = + 0.410V.
The final reaction coming as, Cr2+ + 2e- Cr (s)
Ecell = Ereduction + Eoxidation
Ecell = 0.50 + 0.41 V
Ecell = 0.91 V
G = -nFE
G = - 2x 96486x0.91 J/mole 82
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