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CHE154 (B.

Tech Biotech)

CHE154: Physical Chemistry for Honors


B. Sc. Biotech. Chemistry Course, Term: II, Session: February 2008 – May 2008

Dr. Shikha Baskar


Sr. Lecturer
Department of Chemistry
Lovely Professional University, Phagwara, Punjab, India

Thermodynamics

Venue: 5-308, LPU

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Basic Concepts of Thermodynamics

Thermodynamics and Energy


Definition of Thermodynamics

Thermodynamics is defined as the science of energy.

Engineering thermodynamic deals with the principles of energy


and energy conversion in engineering and the thermal properties
of substances as well.

It can be divided into: Classical Thermodynamics--------macroscopic


approach

Statistical Thermodynamics--------microscopic approach

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Basic Concepts of Thermodynamics

Thermodynamics and Energy

Contents of Thermodynamics

The Basic Laws of Thermodynamics :


(1) The First Law of Thermodynamics:

an expression of the quantity relationship


during energy change

(2) The Second Law of Thermodynamics:

an expression of the quality relationship during


energy change
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Thermodynamics System

The definition of Thermodynamics System


System : A quantity of matter or a region in
space for study
The real or imaginary surface that separates the
system from its surroundings is called boundary
Anything outside the boundary is called
surrounding

The boundary can be real or


imaginary; fixed or
changeable, has no thickness
and volume , and does not
contain any substance.

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The Classification of Thermodynamics system

Closed system :
A system that only energy can cross the
boundary but no mass can enter or leave
( also known as control mass )

Opened system :
A system that not only energy but also mass
can cross the boundary (also known as
control volume )

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Isolated system :

A system that neither energy nor mass can


cross the boundary
(a special closed system)

The Universe

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State and Equilibrium

Definition: All macroscopic characteristics of a system at one time point

Classification:
Equilibrium state:
any part of the system have the same
characteristics
any characteristics don’t change with
time
Nonequilibrium state:
Conditions of Equilibrium
•Thermal equilibrium
•Mechanical equilibrium
•Chemical equilibrium
•Phase equilibrium

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Properties of System

Definition
Any characteristic of a system is called a
property
Characteristic of property
Related with States but have nothing to do with the
path from one state to another

According to ∮dx = 0
mathematics :
Classification of property

Intensive property :
Properties independent of the size of
system, such as :
temperature, pressure, specific volume

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Extensive property :

Properties whose values depend on the size or extent


of system, such as :
volume, entropy, enthalpy

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The state postulate

The state of system is described by its properties,But


obviously we don’t need to specify all the properties to fix
a state,Then how many properties are enough to fix a
state?

State postulate

The state of a simple compressible system is completely


specified by two independent, intensive properties

A system is called simple compressible


system in the absence of electrical,
gravitational, motion, and surface tension
effects.

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Process and Cycle

Process:
any change that a system undergoes from one equilibrium state to another

Quasi-static process:

a process proceeds in such manner that the system remains


infinitesimally close to an equilibrium state at all time
Initial state
p
Quasi-static process

final state
nonequilibrium
process

v
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Cycle:

A path-closed process

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Forms of energy

Total energy
The total energy E of a system is the sum of thermal, mechanical, kinetic,
potential, electric,chemical and nuclear energy.

On a unit mass basis,

e = E/m
1-8-2 Classification of energy
1.Macroscopic form : kinetic energy KE and potential energy PE

mV 2 PE = mgz
KE = and
2
On a unit mass basis

ke =
V2 and pe = gz
2
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Forms of energy

Microscopic form:
relate to the molecular structure of a system and the degree of the
molecular activity. The sum of all the microscopic forms of energy is called
the internal energy, denoted by U or u on a unit mass basis.

1-8-3 Expression of total energy

mV 2
E = U + KE + PE = U + + mgz
2
On a unit mass basis

V2
e = u + ke + pe = u + + gz
2
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Pressure
definition
The force exerted by a fluid per unit area
Calculation:
F
P=
A
Unit:
SI: Pa--------N/m2

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1bar=105 Pa
= 0.1 Mpa
=100 kPa

1atm=101,325 Pa
= 101.325 kPa
=1.01325 bar
=14.696 psi

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Gage pressure and vacuum Pressure

Absolute pressure: the actual pressure at a given position is called the


absolute pressure

manometer

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Gage pressure:The pressure over atmospheric pressure while gas
pressure is larger than that of atmosphere , expressed by Pg

Pg = Pabs − Patm
Vacuum pressure:The pressure below atmospheric pressure
while gas pressure is smaller than that of
atmosphere , expressed by Pv

Pv = Patm − Pabs

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I think it is the measure of Temperature
hotness or coldness
Am I right?

What is
temperature?

1-10-1 The zeroth law of thermodynamics

If two bodies are in thermal equilibrium with a third


body , they are also in thermal equilibrium each other .

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Thermodynamics definition of temperature

It’s the property to describe if systems are in thermal equilibrium

Temperature scale
Three factors of Temperature scale :
• zero point
• two states point ( easily reproducible states )
• Scale

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Formerly called the centigrade scale, in
1948 it was renamed after the Swedish
astronomer A.Celsuis (1701-1744)

Temperature scale in history named after the German


instrument maker G.Fahrenheit
(1686-1736)
SI: Celsius scale

English: Fahrenheit scale

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Thermodynamics temperature scale:

SI: Kelvin scale

English: Rankine scale

Relations of scales:

T (K ) = T (。C) + 273.15
T (R ) = T (。F) + 459.67

T (。F) = 1.8T (。C) + 32


T (R ) = 1.8T (K )
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