Thermodynamics that property (also known as intensives property)

 The science of energy, that concerned with the ways in which

energy is stored within a body.
 Energy transformations – mostly involve heat and work
movements.
 The Fundamental law is the conservation of energy principle:
energy cannot be created or destroyed, but can only be THERMODYNAMIC PROPERTIES
transformed from one form to another. MASS - quantity of matter
WEIGHT - force exerted on a body by gravity
VOLUME - space occupied by matter
SPECIFIC VOLUME - volume per unit mass
SPECIFIC WEIGHT - weight per unit volume
DENSITY - mass per volume of substance
TEMPERATURE - degree of hotness or coldness
PRESSURE force exerted per unit area
SPECIFIC HEAT - energy required to raise or lower tem of
substance about 1 k or 1°C
INTERNAL ENERGY - energy contain within system WORK -
System, surroundings and boundary kind of energy transfer - acting force- flow direction
HEAT- kind of energy transfer - temp difference
 System: A quantity of matter or a region in space chosen for ENTHALPY - total energy of the system (I.E + F.W)
study.
 Surroundings: The mass or region outside the system State, Equilibrium and Process
 Boundary: The real or imaginary surface that separates the  State – a set of properties that describes the conditions of a
system from its surroundings. system. Eg. Mass m, Temperature T, volume V
 Thermodynamic equilibrium - system that maintains thermal,
mechanical, phase and chemical equilibriums.
Type of system  Process – change from one equilibrium state to another.
(Isolated System)
 Isolated system – neither mass nor energy can cross the selected
boundary.
 Example (approximate): coffee in a closed, well-insulated
thermos bottle

The prefix iso- is often used to designate a process for which a

particular property remains constant.
Isobaric process: A process during which the pressure P remains
constant.
(Closed system) Pressure is Constant (ΔP = 0)
 Closed system – only energy can cross the selected Isochoric (or isometric) process: A process during which the
boundary specific volume v remains constant
 Examples: a tightly capped cup of coffee

Properties of a system
Properties of a system is a measurable characteristic of a system that
is in equilibrium.
Properties may be intensive or extensive.
Intensive – Are independent of the amount of mass:
e.g: Temperature, Pressure, and Density,

Isothermal process: A process during which the temperature T

remains constant.

Types of Thermodynamics Processes

Specific properties – The ratio of any extensive property of a system  Cyclic process - when a system in a given initial state goes
to that of the mass of the system is called an average specific value of through various processes and finally return to its initial
state, the system has undergone a cyclic process or cycle.
 Reversible process - it is defined as a process that, once
having take place it can be reversed. In doing so, it leaves
no change in the system or boundary.
  Irreversible process - a process that cannot return both the • If the properties of the system has finite departures from
system and surrounding to their original conditions thermodynamic equilibrium path the process is said to be non quasi
 Adiabatic process - a process that has no heat transfer into static
or out of the system. It can be considered to be perfectly • Quasi static process is the succession of thermodynamic equilibrium
insulated. state while in case of non-quasi static process the end states only
 Isentropic process - a process where the entropy of the represent the thermodynamic equilibrium.
fluid remains constant.
 Polytropic process - when a gas undergoes a reversible Condition for reversible process are
process in which there is heat transfer, it is represented with 1. No Friction
a straight line, PVn = constant. 2. Heat transfer is through infinitely temperature difference.
 Throttling process - a process in which there is no change 3. There are no spontaneous changes in the system.
in enthalpy, no work is done and the process is adiabatic. • All processes in nature are irreversible.
Work done in moving boundary of close system in quasi-static
process displacement work
Zeroth Law of Thermodynamics • Force Exerted on piston, F =
PA
“ If two bodies are in thermal equilibrium with a third body, there
• Small work done, δw = F dl
are also in thermal equilibrium with each other.”
δw = P A dl
δw = P Dv

Point Function
When two co-ordinates are located on the graph, They define a point
and the two properties on the graph define state. These properties (p,
T, v) are called point function. Heat
• Heat is the form of energy which transfer without transfer of mass,
Path Function from one body to another body (or between system and
There are certain quantities like heat and work can not be located on a surroundings) from higher temperature to lower temperature by
graph by a point but there are represented by the area. It is not a state virtue of temperature difference between two bodies.
or point function, rather it depends on the path of the process. Such • Abbreviated as ‘Q’ and Unit is J (Joule)
quantities are called path function and they are inexact differentials • Heat Addition into system :- Positive ( +Q)
Process • Heat Rejection from system :- Negative (-Q)
1. If any one or more properties of the system undergo a • Extensive Property and Path Function (Inexact Differential)
change due to energy or mass transfer we say that the
system has undergone a change of state Work
2. The successive change of state of the system due to •Analogous to heat, work is also a transient form of energy which is
energy or mass transfer defined by definite path is observed when it crosses the boundaries of the system without
called a process. transfer of mass.
3. The curve joining the successive state represents the • It is Path Function
process path • Small work done due to displacement ds
4. If a system undergoes two or more processes and
returns to its original state after conclusion of
processes, the system is said to have undergone a cycle
Difference between heat and work
Thermodynamic equilibrium 1. Heat can only transfer when there is difference of temperature
• A system is said to be in thermodynamic equilibrium which is between the system and surrounding, while work transfer can take
incapable of any spontaneous change of its macroscopic properties place even without the change in temperature
(p, v, t) and it is in complete balance with its surroundings. 2. In constant volume process though work can not take place,
• A system will be in thermodynamic equilibrium if it satisfies the however
condition of mechanical, thermal and chemical equilibrium heat can be transferred.
1. Mechanical equilibrium :- No unbalance forces 3. In case of work transfer, its sole effect could be raising or lowering
2. Thermal Equilibrium :- Uniformity of temp. inside with a weight in the surrounding but in case of heat transfer other effects
surrounding are also observed.
3. Chemical Equilibrium :- Absence of any chemical Similarities between heat and work
reaction 1. Both heat and work exist in transit and these are never possessed or
Quasi Static Process / Reversible contained in a system.
• A quasi static process is defined as a process in which the properties 2. Both heat and work refer to boundary phenomena.
of the system depart infinitesimally (extremely small) from the 3. Both heat and work are path function and do not represent as the
thermodynamic equilibrium path
properties of system (Inexact difference, 𝛿𝑥 ) (First Law of Thermodynamics)
Enthalpy
• It is total energy of the system First Law Sign Conventions
• Specific Enthalpy, Heat is added to the system + Work on the system +
• U, p, V are point function, so H is point function and property of Heat is lost - Work done by the system -
system
• Unit of Enthalpy (H) is kJ Second Law of Thermodynamics
• Unit of Specific Enthalpy (h) is kJ/kg • Kelvin Planck statement: "It is impossible to construct a heat
H = U + pV engine working in a cyclic process, whose sole effect is to convert the
h = u + pv heat energy supplied into equivalent amount of work. It means that
heat engine cannot fully convert the heat supplied into mechanical
Enthalpy work." (Applicable for heat engine)
• It is Total heat content of the system and defined as energy which is • Clausius statement: "It is impossible for machine (heat pump or
algebraic sum of internal energy and flow work. refrigerator) to transfer heat from a body at low temperature to a body
H=u+PVs kJ/Kg Where H= Total Enthalpy at high temperature to a body at high temperature, without aid of
u = Internal Energy external source." (Applicable for heat Pump & Refrigerator)
P = Absolute Pressure

Entropy
It means Transformation.
Entropy is a thermodynamic property of a working substance which
increases with the addition of heat and decreases with removal of
heat. Entropy is represented by symbol S or .
Change in Entropy = dQ / T
Where,
T= Absolute temperature dQ = Change in heat
AS = Change in Entropy Unit of Entropy KJ/Kg0K

First law of thermodynamic (Energy conservation law)

•“Energy can neither be created nor-destroyed but it can be converted
from one form to another."
First law of thermodynamic applied to close System, Cyclic Process
Laws of Thermodynamics
If a close system goes through a cycle, the algebraic sum of total
The Three Laws of Thermodynamics
energy transfer to it as heat and work is zero.
-The first law of thermodynamics, also called conservation of
energy. We can use this knowledge to determine the amount of energy
in a system, the amount lost as waste heat, and the efficiency of the
Limitations of the first law of thermodynamics
system.
1. No restriction on the direction of the flow of heat: the first law
-The second law of thermodynamics states that the disorder in the
establishes definite relationship between the heat absorbed and the
universe always increases. As the disorder in the universe increases,
work performed by a system. The first law does not indicate whether
the energy is transformed into less usable forms. Thus, the efficiency
heat can flow from a cold end to a hot end or not. For example: we
of any process will always be less than 200%
cannot extract heat from the ice by cooling it to a low temperature.
-The third law of thermodynamics tells us that all molecular
Some external work has to be done.
movement stops at a temperature we call absolute zero, or D Kelvin
2. Does not specify the feasibility of the reaction: first law does not
(-273°C). Since temperature is a measure of molecular movement,
specify that process is feasible or not for example: when a rod is
there can be no temperature lower than absolute zero. At this
heated at one end then equilibrium has to be obtained which is
temperature, a perfect crystal has no disorder.
possible only by some expenditure of energy.
3. Practically it is not possible to convert the heat energy into an
equivalent amount of work.
Third Law of Thermodynamics
■ Another fundamental principle of thermodynamics which deals
AU = Q + W
with the entropy of pure crystalline substance at the absolute zero of
AU is the change in internal energy of the system, Q is the heat added
temperature, has come into being, the principle called the third law of
to the system, and W is the work added to the system (or done on the
thermodynamics, states that:
system).
■the entropy of all pure crystalline solids may be taken as zero at
Q is positive when it is added to the system and negative if it is taken
the absolute zero of temperature.
out of the system.
■ The statement is confined to pure crystalline solids because
Wis positive if it is added to the system and negative if it is done by
theoretical argument and experimental evidence have shown that the
the system. This means that the work done by an engine that uses heat
entropy of solutions and super cooled liquids is not zero at 0°K.
is negative. Think of it as being negative because it is leaving the
system.
We all know about Volume.
output work is negative
Pressure:
input work is positive
Pressure = Force / Area
Example
120 lb woman putting all her weight on 2in2 of heals.
Pressure = 120 lb/2in2 = 60 lb/in2. Is that a lot?
Comparison: 1 atm = 14.7 lb/in 2. Thus of heals is approximately 4
atm. This is the pressure you would feel at a depth of approximately
133 ft of water.

Construction of a Temperature Scale

Choose fixed point temperatures that are easy to reconstruct in any
lab, e.g. freezing point of water, boiling point of water, or anything
else you can think of.

Fahrenheit: Original idea:

0°F Freezing point of Salt/ice
100°F Body Temperature
Using this ice melts at 32°F and water boils at 212°F (Not overly
convenient) Note: 180°F between boiling an freezing.

Celsius (Centigrade) Scale: Example Calculation

0°C Ice Melts 100°C Water Boils - Compare the amount of heat energy required to raise the
Note a change of 1°C = a change of 1.8°F. temperature of 1 kg of water and 1 kg of iron 20 °C?
Q=mCAT
For Water
Conversion between Fahrenheit and Celsius Q = (1000g)(1cal/g°C)(20°C) = 20,000cal
If we know Celsius and want Fahrenheit (F = (9/5) C+32) For Iron
If we know Fahrenheit and want Celsius (F = (5/9) F-32) Q = (1000g)(0.107cal/g°C) (20°C) =2, 140cal

Absolute or Kelvin Scale Laws Of Perfect Gas

The lowest possible temperature on the Celsius Scale is -273°C. 1) Boyle's law- "The absolute pressure of a given mass of perfect gas
The Kelvin Scale just takes this value and calls it OK, or absolute varies inversely as its volume, when the temperature remain
zero. constant".
Note: the "size" of 1K is the same as 1°C. Mathematically PV = constant (T= const.)
To convert from C to K just add 273. (K = C+273) 2) Charles law- "The volume of a given mass of a perfect gas varies
directly as its absolute temperature, when the pressure remains
constant". Mathematically, V/T constant (p= const.)
3) Gay-lussac law- "The absolute pressure of a given mass of a
perfect gas varies directly as its absolute temperature when volume is
constant." Mathematically, P/T = constant (v= const.)

THERMODYNAMIC PROCESS
Here is a brief listing of a few kinds of processes, which we will
encounter in TD:
>Isothermal process → the process takes place at constant
temperature
(e.g. freezing of water to ice at -10°C)
Units of Heat >Isobaric → constant pressure (e.g. heating of water in open air →
Heat is a form of energy so we can always use Joules. under atmospheric pressure)
More common in thermodynamics is the calorie: By definition 1 > Isochoric → constant volume (e.g. heating of gas in a sealed metal
calorie is the amount of heat required to change the temperature of 1 container)
gram of water 1°C. 1 Cal = 1 food calorie = 1000 cal. >Reversible process → the system is close to equilibrium at all
times (and infinitesimal alteration of the conditions can restore the
The English unit of heat is the Btu (British Thermal Unit.) It is the universe (system + surrounding) to the original state.
amount of heat required to change the temperature of 1 lb of water >Irreversible Process: The reversal of the process leaves some trace
1°F. on the system and its surroundings.
Conversions: >Cyclic process → the final and initial state are the same. However,
1 cal =4.186 J 1Btu = 252 cal q and w need not be zero.
>Adiabatic process → dq is zero during the process (no heat is
Units of Specific Heat added/removed to/from the system)
C = Q /mAT = cal/g°C = J/kg°C
Note that by definition, the specific heat of water is 1 cal/g°C. Thermodynamics processes of Perfect Gas
1) Const. Volume/ isochoric process: -Temperature and Pressure
will increase
-No change in volume and No work done by gas
-Governed by Gay-Lussac law
2) Const. Pressure/ isobaric process:
- Temperature and volume will increase
- Increase in internal energy Governed by Charles law
3) Constant temperature/ isothermal process:
- No change in internal energy
- No change in Temperature
- Governed by Boyles law (p.v = constant)
4) Adiabatic/ isentropic process:
- No heat leaves or enters the gas Q = 0,
- Temperature of the gas changes
- Change in internal energy is equal to the work done
5) Isentropic process:
- Entropy remains constant dS = 0,
- Temperature of the gas changes
- Change in internal energy is equal to the work done
5) Polytropic process:
- It is general law of expansion and compression of the gases.
p.v^n = Constant
6) Free expansion:
- When a fluid Is allowed to expand suddenly into a vacuum chamber
through on orifice of large dimensions.
Q = 0, W = 0, and dU = 0.

=== The End for Thermodynamics ===