CHAPTER # 11: HEAT &
THERMODYNAMICS
Introduction
• Heat is a form of energy that is in transit. (SI unit is ‘Joules’ & CGS unit is ‘calories’)
• Temperature is a measure of degree of hotness or coldness of a body.
• Change of temperature affects the physical state of matter.
• Effects of Temperature
o Change of color
o Change of state
o Change of resistance
• Major Types of Thermometer
o Mercury glass thermometer
o Bimetallic thermometer
• Any substance that changes uniformly with temperature can be used as thermometric
substance
in thermometer.
• Mercury is preferred as thermometric substance because
o It is non-wetting
o Its expansion is quite linear.
o Boiling point is high
Conversion formula of temperature scales
o TC =
(TF – 32)
o TF = 9/5 TC + 32
o TK = 273 + TC
o TK = 273 + 5/9 (TC – 32)
o TC = TK – 273
o TF = 9/5 (TK – 273) + 32
Important Temperature Conversion
DESCRIPTION K °C °F
Boiling Point of water 373 100 212
Freezing point of water 273 0 32
Normal body temperature 310 37 98.6
Absolute zero 0 -273 -459.6
• Absolute zero is a temperature at which if gases remain in gaseous form, exert zero pressure
and
have zero volume.
• Heat flows from one body to another due to temperature difference.
• Temperature determines the direction of natural flow of heat.
• Internal energy or thermal energy is the sum of KE and PE of all molecules of a body.
• When excess of thermal energy flows from one body to another, as heat, then it is converted
into
internal energy.
DO YOU KNOW?
Celsius degree is larger than a
Fahrenheit degree by a factor of 9/5
DO YOU KNOW?
The Centigrade and Fahrenheit scale
shows the same reading at a temperature
of -40°C.
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Kinetic Molecular Theory of Gases (K.M.T.)
Main points of K.M.T. of gases are given as:
o Small volume contains large number of molecules.
o Molecules move randomly and do not exert force on one another except when they collide.
o Molecules collide with each other elastically.
o The collisions with walls give rise to gas pressure.
o Gravity does not affect the molecular motion.
o Volume of gas molecules this negligible this compared to the actual volume of the gas.
THERMAL EXPANSION
Bodies undergo change in size when they are heated. This change in size on heating is termed
Thermal Expansion.
LINEAR EXPANSION: Expansion of length of solids on heating is called linear expansion.
Change in length ∆L = α Lo ∆T
Where α = coefficient of ∆L, Lo = initial length ∆L = change in length
Final length: L’ = Lo (1 + α ∆T)
Where ∝ is a constant of proportionally which depends upon the material of rod and is called
the
co-efficient of linear expansion.
∝=
∆L
L∆T
∝ is defined as the change in length per unit length per Kelvin rise in temperature. Its unit is K
−1
VOLUME EXPANSION: The solids expand on heating in all the three dimensions i.e. length,
breadth
and thickness.
∆V ∝ V∆T
∆V = β V ∆T
Where β is co-efficient of volume expansion. It is defined as Fractional Change in Volume per
unit
change in temperature. Its unit is also K
−1
. (Note that β = 3 ∝)
BIMETALLIC THERMOSTAT: Thermostats are well known devices commonly used for maintaining
required temperatures. A common type of thermostat called Bimetallic Thermostat.
The Bimetallic strip works as an electric contact breaker in an electrical heating circuit.
THERMAL CONDUCTIVITY: Thermal conductivity of a substance is a measure of its ability to
conduct heat energy. The amount of heat (∆Q) flows through on object is
∆Q = K A T ∆t
∆L
Where
o K = thermal conductivity
o A= Areas of cross- section
o ∆t = change in temperature
o T = Time interval
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o ∆L = Change in length
In S I unit it Is measured in J/sec. m 0C. It is large for metals & small for non-metallic solids,
liquids &
gases.
GAS LAWS
BOYLE’S LAW:
For a given mass of a gas, at constant temperature, the volume is inversely proportional to the
pressure. Graph between (P) & (V) is Hyperbolic curve while graph between (P) & (1/V) is a
straight line.
PV = constant
CHARLES’S LAW:
For a given mass of a gas, at constant pressure, the volume is directly proportional to the
temperature. Graph between (V) and (T) is a straight line.
V/T = constant
GENERAL GAS LAW
General gas law is the combination of Boyle’s, Charles’s & Avogadro’s law i.e. the two equations
P1 V1
T1
P2 V2
T2
PV= nRT
Pressure and Temperature of an Ideal Gas
The Kinetic theory of the gases is the study of the microscopic behavior of molecules and the
interactions which lead to microscopic relationships like the ideal gas law.
P=
Ρ̅V
2 = 1/3*(RHO)*(MEAN SQUARE VELOCITY)
P=
NV M̅V
(SINCE Ρ = M NV)
BOLTZMANN CONSTANT (K):
Boltzmann Constant = Universal Gas Constant / Avogadro Number
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K = R/NA= 1.38 X 10−23
J / (MOLECULES – K).
Equation of State: P V = N K T
RELATION B/W AVERAGE TRANSLATIONAL K.E. (ATKE) & ABSOLUTE TEMPERATURE: -
2
mV̅2 =
KT
ATKE ∝ T
AVERAGE TRANSLATIONAL KINETIC ENERGY PER MOLECULE:
ATKE(MOLECULE) =
KT
AVERAGE TRANSLATIONAL KINETIC ENERGY PER MOLE:
ATKE(MOLE) =
RT
Specific Heats
• Amount of heat required to raise the temperature of a substance through 1 K is called heat
capacity. It is measured in J/Kg.
Q = CHC ∆T
• Specific heat capacity is the amount of heat required to raise the temperature of unit mass (1
Kg
in SI or MKS System / 1 gram in CGS System) through unit temperature. It is measured in J/Kg-K.
Q = m CSP ∆T
• Molar Specific Heat Capacity is the amount of heat required to raise the temperature of one
mole
of a substance through unit temperature. It is measured in J/Mole-K.
Q = m CMHC ∆T
• There are two kind of molar specific heat of a gas.
o Molar specific heat at constant volume.
o Molar specific heat at constant pressure
• Avogadro’s law states
“Equal volumes of gases at same temperature and pressure contain equal number of
molecules.”
• Law of Heat of Exchange:
“If no heat is lost to surroundings or gained from it, then
Heat Loss = Heat Gained.”
LATENT HEAT: Quantity of heat required to change the state of a substance (having unit mass) at
constant temperature (Q = mH) where H is Latent Heat measured in J/Kg.
LATENT HEAT OF FUSION: It is the quantity of heat required to transform one kg of ice
completely
into water at 00C.
Hf =
∆Q
LATENT HEAT OF VAPORIZATION: It is the quantity of heat required to transform one kg of water
completely into steam at 1000C.
Hv =
∆Q
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Calorie: Unit of heat energy. it is defined as, the amount of heat required to raise the
temperature of
one gram of water from 14.5 0C to 15.5 0C
1 Calorie = 4.2 joule
Effect of Pressure On Melting Point: Increase of pressure lowers the freezing point of water.
Effect of Pressure On Boiling Point: Decrease in pressure lowers the boiling point of liquid.
Introduction to Thermodynamics
Thermodynamics is the study of relationship between heat and other forms of energy.
o Thermodynamics states derives the states of a system.
o Any collection of matter having distinct boundaries is called a system.
o Sum of translational KE, rotational KE, vibrational KE and PE is called internal energy.
o Internal energy of an ideal gas system is generally the translational KE of its molecules.
o Increase in temperature of the object is an indication of increase in the internal energy.
o Internal energy is similar to the gravitation PE.
o Work done on a system in which gas is enclosed as written as W = P∆V.
LAWS OF THERMODYNAMICS
Thermal Equilibrium:
It is observed that a higher temperature object which is in contact with a lower temperature
object
will transfer heat to the lower temperature object. The objects will approach the same
temperature,
and in the absence of loss to other objects, they will then maintain a constant temperature.
They are
then said to be in thermal equilibrium. Thermal equilibrium is the subject of the Zeroth Law of
Thermodynamics.
ZEROTH LAW OF THERMODYNAMICS
The “Zeroth Law” states that if two systems are at the same time in thermal equilibrium with a
third
system, they are in thermal equilibrium with each other.
If A and C are in thermal equilibrium with B, then A is in thermal equilibrium with B. Practically
this
means that all three are at same temperature, and it forms the basis for comparison of
temperatures. It is so named because it logically precedes the First and Second laws of
Thermodynamics.
FIRST LAW OF THERMODYNAMICS (Law of conservation of energy)
When heat is transformed into other forms of energy total heat energy remains constant.
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∆Q = ∆U + W
SIGN CONVENTION:
Amount of Heat:
o If heat is supplied to the system (absorbed), ∆Q is taken Positive.
o If heat is given by the system (released), ∆Q is taken Negative.
Work done:
o If work is done by the system, then +ve Work done is considered (Expansion or Change in
volume is +ve)
o If work is done on the system, then -ve Work done is considered (Compression or Change in
volume is -ve)
Change in Internal energy:
o If internal energy of the system increases, ∆U is taken Positive.
o If Internal energy of the system decreases, ∆U is taken Negative.
Inferences from 1st Law of Thermodynamics
• Change in internal energy = Heat energy flowing in - Energy flowing out as mechanical work
∆U = ∆Q - ∆W
• Internal energy is a state function i.e. depends on initial and final states.
• For a cyclic system, we have
∆U = 0
Ui = Uf
∆Q = ∆W
Applications of 1st Law of Thermodynamics
• Isothermal Process: is that in which temperature remain constant
∆Q = ∆W ∆U = 0
• Isochoric Process: is that in which volume remains constant.
∆Q = ∆U ∆W = 0
• Isobaric Process: is that in which pressure remains constant.
∆Q = ∆U + P∆ V
• Adiabatic Process: is that in which no heat enters or leaves the system. (Q=0)
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Note: Cooling is produced when adiabatic expansion takes place and heating is produced during
that adiabatic compression.
Adiabatic process is also termed as iso-entropic process. i.e. a process in which the entropy of
the
system remains constant.
Graphical Representation
Thermodynamic Processes
Process Definition of
Process
Equation of
Process
1st law applied to it
(Q = ∆U + W)
Isothermal Constant temperature PV = Constant ∆U = 0, (Q = W)
Isobaric Constant pressure V/T = Constant W = P∆ V
(Q = ∆U + P∆V)
Isochoric Constant volume P/T = Constant ∆V = 0
(Q = ∆U)
Adiabatic No Heat Supplied to
the system
PV = Constant Q = 0
(+∆U = -W) & (-∆U = +W)
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Note: CP is greater in value than CV
• QV = n CV ∆T (Heat supplied at constant volume)
• QP = n CP ∆T (Heat supplied at constant pressure)
• CP – CV = R
• CP / CV = γ
• For monatomic gases: CP =
5R
and CV =
3R
• For diatomic gases: CP =
7R
and CV =
5R
SECOND LAW OF THERMODYNAMICS
o Kelvin Statement (Heat Engine Statement)
“It is impossible to construct a heat engine which converts all heat energy absorbed from
source without having a sink.”
o Clausius’s Statement (Refrigerator Statement)
“It is impossible to transfer heat from cold to hot region without expenditure of external
energy.”
Refrigerator
A refrigerator is a heat engine in which work is done in a refrigerant substance in order to
collect
energy from a cold region and exhaust it in a higher temperature region, thereby further cooling
the
cold region.
Heat Engine
Heat engine is a thermo-device, which converts heat energy into mechanical energy.
• There exists no perfect engine.
• Heat engine always operates in a cycle.
• Cycle means set of changes, which bring a system to its initial state.
Carnot Heat Engine
• Saudi Carnot proposed it in 1840. (Ideal Engine)
• Carnot Heat Engine has maximum efficiency, but not 100%.
ηc = (1 – T2/T1) × 100
• Carnot cycle consists of following processes
1) Isothermal Expansion
2) Adiabatic Expansion
3) Isothermal compression
4) Adiabatic compression
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Following things should be kept in mind about efficiency about Carnot engine:
o It depends upon ∆T.
o It is independent of working substance.
o It is 100% only when T2 = 0K OR Q2 = 0J (Both the cases are not possible)
ENTROPY
Entropy is a measure of molecular disorder and in any process the entropy increases or remains
constant, that is the disorder increases or remains constant. The degree of delocalization is a
measure of disorder. Entropy or disorder always increases or remains constant.
• Degree of disorderliness is called statistical entropy.
• Unavailability of heat energy is called thermo entropy.
• Law of increase of entropy
“Entropy of a thermodynamic system is either remains constant (during reversible process) or
it increases (during irreversible process).”
• We can represent change in entropy by following relation;
∆S = ∆Q/T
Where ∆S is positive if heat enters and vice versa
• Its unit is J/K.
• Entropy may remain constant for a reversible process.
• Entropy increases for all irreversible processes.
Entropy: A state variable whose change is defined for a reversible process
at T where Q is the heat absorbed.
Entropy: A measure of the amount of energy which is unavailable to do
work.
Entropy: A measure of the disorder of a system.
Entropy: A measure of the multiplicity of a system. (Point to ponder)
DO YOU KNOW?
The area under the PV
diagram gives us the
work done by the
engine.
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Environmental Crisis as Entropy Crisis
• Entropy is a time arrow.
• Increase of entropy leads to heat death of universe because of thermal pollution because of
inevitable consequence of second law of thermodynamics.
• Environmental crisis is an entropy or disorder crisis resulting from our future efforts to ignore
the 2nd law of thermodynamics.