LESSON 1

Basics of Thermodynamics

 The word "thermo-dynamic", used first by Thomson has Greek origin and is translated as the combination
of
 therme : heat
 dynamis : power

 Thermodynamics is the science that deals with heat and work and those properties of matter that relate
to heat and work.

 It deals with energy changes in physical and chemical processes.

Historical Milestones

 first century AD: Hero of Alexandria documents many early thermal engines.
 1593: Galileo develops a water thermometer.
 1650: Otto von Guericke designs and builds the first vacuum pump.
 1662: Robert Boyle develops his law for law for isothermal ideal gases.
 1679: Denis Papin develops his steam digester, forerunner to the steam engine.
 1698: Thomas Savery patents an early steam engine.
 1710: Thomas Newcomen creates a more practical steam engine.
 1760s: Joseph Black develops calorimetry.
 1780s: James Watt improves the steam engine.
 1798: Benjamin Thompson (Count Rumford) considers the mechanical equivalent of heat from cannon
boring experiments.
 1824: Nicolas Leonard Sadi Carnot discusses idealized heat engines.
 1840: Germain Henri Hess considers an early version of the first law of thermodynamics for work-free
chemical reactions.
 1840s: Julius Robert von Mayer relates heat and work.
 1840s: James Prescott Joule relates heat and work.
 1847: Hermann von Helmholtz publishes his theory of enrgy conservation
 1848: William Thomson (Lord Kelvin) postulates an absolute zero of temperature.
 1850: Rudolf Julius Emanuel Clausius formalizes the second law of thermodynamics.
 1865: Clausius introduces the concept of entrophy.
 1871: James Clerk Maxwell developd the Maxwell relations.
 1870s: Joslah Willard Gibbs further formalizes mathematical thermodynamics.
 1870s: Maxwell and Ludwig Boltzmann develop statistical thermodynamics.
 1889: Gibbs develops statistical mechanics, giving underlying foundations for classical and statistical
thermodynamics.
Some practical applications
 Hero of Alexandra
 Denis of Papin
 Comet - the first commercial steam vessel
 Steam Locomotive, Rocket (Robert Stephenson)
 Power Plant

Some concepts and definitions

System
 may be defined as the part of universe selected for thermodynamic consideration i.e. to study the
effect of temperature, pressure, etc.
 it may also be defined as specified part of universe in which energy changes are taking place.

Surrounding
 The remaining portion of universe excluding the system is called Surrounding
 Universe = System + Surrounding
 The System and Surrounding can be separated by real and imaginary boundary

Types of System

1. Open system: Here mass and energy can be exchanged with surroundings eg. If some water is kept in open
vessel of hot tea in open cup.
2. Closed System: In a closed system, there is only the exchange of energy with surroundings, no exchange of
mass takes place. For example, if water is placed in closed metallic vessel or hot tea placed in closed tea pot.
3. Isolated System: There is neither exchange of mass nor energy with surrounding. For example, water placed
in a vessel which is closed as well as insulated or tea placed in a thermos flask.

Classification of system on the basis of nature of constituents

Homogeneous System: All the constituents are present in the same phase and composition of system is
uniform throughout.

Heterogeneous System: It contains two or more phases and the composition is not uniform throughout.

Intensive Properties
 They do not depend on the size of the system or quantity of matter present in it.
 They are dependent on the nature of substance present in it.
 Example: pressure, temperature, density, surface tension
Extensive Properties
 Depend on the quantity of matter present in the system
 Example: volume, energy, heat capacity, entropy

Heat capacity: the amount of energy needed to raise the temperature of substance by 1 degree celcius

State of System
 They are the condition of system which is described in terms of certain measurable properties such as
temperature (T), pressure (P), volume (V) etc. of the system.

State Variables
 The properties of system such as temperature (T), pressure (P), volume (V) when changed, the system
also changes.

State Function
 It is defined as the property whose values depends only upon the state of the system and is
independent of the path by which state has been reached.
 For example: a person standing on the roof of the building has a fixed value of potential energy and teh
potential of person does not depend whether he has reached there by stairs or lift. Ex. Potential
energy, pressure, volume, temperature, internal energy, etc.

Process
 when state of system changes then process is said to occur
 the first and last state of process are initial and final state respectively
 Process give us the path by which system changes from one state to other
 There are certain processes in which particular state variable is kept constant

Types of Process

Isothermal Process
 It is defined as the process in which temperature of system remains constant.
 Heat can flow from system to surrounding and vice versa in order to keep the temperature constant

Adiabatic Process
 The system does not exchange heat with the surrounding
 System is completely insulated from surrounding

Isochoric Process
 Volume of system remains constant during the process
Isobaric Process
 Here pressure of the system remains constant during the process

Cyclic Process
 Here the system undergoes series of changes and finally returns to its initial state

Reversible Process
 Such a process is carried out infinitesimally slowly so that all changes occurring in the direct process
can be reversed and the system and the surrounding remain in state of equilibrium
 It is an ideal process and cannot be realized in actual process

Irreversible process
 Change is brought about rapidly and the system does not attain equilibrium
 The force which drives the reactants towards products is greater than opposing force which is to carry
reverse process

Spontaneous process
 It may also be defined as the process which can take place by itself or initiation
 Which take place by itself
o Evaporation of water in open vessel
o Dissolution of salt in water
o Flow of water down a hill
 Which take place by initiation
o Combination of oxygen and hydrogen to form water
o Lighting of candle is initiated by ignition

Non Spontaneous Process

 It is the process which cannot take place by itself or initiation
 Examples:
o Flow of heat from cold body to hot body
o Flow of water up the hill
o Dissolution of sand in water

Some Thermodynamic Quantities

Internal Energy
 Every system is associated with a definite amount of energy, which is called its internal energy. It is
donated by E or U
 It depends upon the various factors such as temperature, pressure and chemical nature of the
substance
  Change in Internal Energy
o The change in internal energy in a chemical reaction is the difference in the internal energies of
the products and the reactants
∆E= E(products)-E(reactants)
= Ep-Er

Enthalpy(H)
 Enthalpy or heat content of a system may be defined as the sum of the internal energy and the product
of its pressure and volume
H =E + PV
 Where E is the internal energy
o P is pressure
o V is the volume of the system
 Change In Enthalpy
o It is the difference in the enthalpies of the products and the reactants
∆H = H(products)- H(reactants)
= H p- Hr

Entropy
 It is a measure of the randomness or disorder of the system
 The greater the randomness, the greater the entropy
 Entropy of a crystalline substance is minimum in the solid state and maximum in the gaseous state
 Melting of ice is an example of increasing entropy
 It is represented by S
 It depends on temperature and increases with increase in temperature
 The change in entropy is equal to heat absorbed isothermally and reversibly during a process divided
by absolute temperature at which heat is adsorbed
∆ S = q rev/T

There are four Laws of thermodynamics:

1. Zeroth law of thermodynamics

 When two bodies A and B are separately in thermal equilibrium with a third body, they in turn are in
equilibrium with each other

2. 1st Law of thermodynamics

 Energy can neither be created nor destroyed although it may be converted from one form to other
 The total energy of the universe remains constant although it may undergo transformation from one
form to other
 The energy of an isolated system remains constant
 ∆U= q + W
 Where
o ∆U = change in internal energy
o q = heat energy
o W = work done

3 2nd Law of thermodynamics

 All spontaneous or naturally occurring processes are irreversible
 Without the help of an external agency a spontaneous process cannot be reversed thermodynamically
 The entropy of an isolated system must increase if it is to be spontaneous
 In an non isolated system the total energy of both the system and surrounding must increase or must
be positive
 The total entropy of the universe must tend to increase in a spontaneous process
∆S (total) = ∆S system + ∆S surrounding

3. 3rd Law of thermodynamics

 The entropy of all perfectly crystalline solids may be taken as zero at the absolute temperature
 At absolute zero a perfectly crystalline solid has a perfect order of its constituent particles i.e. there is
no disorder at all. Hence absolute entropy is taken as zero
 LESSON 1
Basics of Thermodynamics

Newton's law states that “the acceleration of a particular body is directly proportional to the resultant force
acting on it and inversely proportional to its mass”

Where k is the proportionality constant

Systems of units where k is unity but not dimensionless:

 cgs system: 1 dyne force accelerates 1 g mass at 1 cm/s2

 mks system: 1 newton force accelerates 1 kg mass at 1 m/s2

 fps system: 1lb force accelerates 1 slug mass at 1 ft/s2

Systems of units where k is not unity

If the same word is used for both mass and force in a given system, k is neither unity nor dimensionless.

 1 lb force accelerates a 1 lb mass at 32.174 ft/s2

 1 g force accelerates a 1 g mass at 980.66 cm/s2

  1 kg force accelerates a 1 kg mass at 9.8066 m/s2

Relation between units of force

 Kilogram force and Newton

 Pound mass and slug

ACCELERATION
A unit of force is one that produces unit acceleration in a body of unit mass.
MASS and WEIGHT
The mass of a body is the absolute quantity of matter in it.
The weight of a body means the force of gravity Fg on the body.

Note: At or near the surface of the earth, k and g are numerically equal, so are m and F g

Specific Volume, Density and Specific Weight

The density p of any substance is its mass (not weight) per unit volume.

The specific volume v is the volume of a unit mass.

The specific weight y of any substance is the force of gravity on unit volume.

Note: At or near the surface of the earth, k and g are numerically equal, so are p and y.

Pressure is defined as force exerted per unit of surface area

Laboratory Devices for Measuring Pressure - Mercury barometer

Two types of Manometer.

A close-end manometer with an evacuated flask attached has the mercury levels equal
A gas exerts pressure on the mercury in the arm closer to the flask. The difference in heights ( h) equals the
gas pressure the gas pressure.
An open-end manometer Is shown with gas pressure equal to atmospheric pressure
Manometer

 If the absolute pressure is greater than atmospheric than atmospheric pressure:

Where
p = absolute pressure
p0 = atmospheric pressure vacuum
pg= gage pressure (due to the liquid column)

 If the absolute pressure is greater than atmospheric than atmospheric pressure:

The gage reading is called vacuum pressure or the vacuum.

Gage Pressure (open to atmosphere)

AtmosphericPressure
Barometer – a device used to measure atmospheric pressure
Temperature
MP
BP

Conservation of Mass
 The Law of Conservation of Mass states that mass is indestructible
 To determine the quantity of fluid passing thru a given section: