CHAPTER # 11( HEAT & THERMODYNAMICS ) 1

(GOLDEN POINTS)
Old concept about Heat / Caloric theory: Up to the beginning of nineteenth century heat was considered as a weightless
fluid called caloric which existed in every material body. Caloric theory could explain processes like conduction,mixing of
substance in calorimeter etc.
Count Rumford first noticed that caloric theory could not explain the production of heat by friction, James Joule further
proved him by discovering the relationship between Mechanical work and heat produced. W=JQ, where J is called
Mechanical equivalent of Heat and it is defined as amount of mechanical work to produce 1 cal of heat. J=4.18 Joules/cal
Heat is a form of energy which is transferred between a system and its surrounding as a result of temperature difference only.
The temperature of a body is a state which determines the direction of flow of heat or the degree of hotness of a body.
Heat content of a body is the total molecular energy where as temp. refers to ave translational K.E
Two bodies containing the same amount of heat may be at different temperatures.

Two bodies at the same temperature may contain different amounts of heat.
The direction of flow of heat from a body does not depend on its heat content but depends on its temperature.
Zeroth Law of Thermodynamics When two systems are in thermal equilibrium with a third system, then they are in thermal
equilibrium with each other.
In principle, any system whose properties change the temperature can be used as a thermometer.

There are generally three scales of temperature. They are Celsius scale, Fahrenheit scale and
Kelvin (or Absolute or thermodynamic temperature) scale.

The most fundamental scale of temperature called Ke lvin scale is based on the laws of thermodynamics.

The melting point of ice at standard atmospheric pressure is taken as the lower fixed point.

The boiling point of water at standard pressure is taken as the upper fixed point.
The distance between the lower and upper fixed points is divided into definite equal divisions.

The reading on one scale can be readily converted into corresponding one or the other by the relation

0 0
K − 273
_______ C F − 32
= ___ = _____
−

100 100 180

The differences of temperature on different scales can be converted using the formula

ΔK ΔC Δ F ΔR
= = =
100 100 180 180
Different types of thermometers and their ranges :

Clinical thermometer –95°F to 110°F 100oC o

212 F 373.15 K
Mercury thermometer −39°C to 357°C
0oC 32oF 273.15 K
Alcohol thermometer − 110°C to 78°C

-273.15 -460 0
Celsius Fahrenheit Kelvin
(C) (F) (K)
Advantages of mercury as a thermometric fluid.

i) Mercury remains as a liquid over a wide range of temperature

ii) Pure mercury can be readily and easily obtained.
iii) Its vapour pressure at ordinary temperature is negligible.
iv) It has high conductivity and low thermal capacity. So it quickly attains the temperature of the body by
taking a negligibly small quantity of heat.
v) It does not wet glass and is opaque.

To have more surface contact with heat, the thermometric bulb will be in the shape of a cylinder.
In clinical thermometers constriction is used so that mercury does not fall back immediately.
Centigrade and Fahrenheit show same reading on -400 but centigrade and Kelvin scale never conside

Temperatures on the Celsius scale denoted by the symbol °C (read “degrees Celsius”). Temperature
changes and temperature differences on the Celsius scale are expressed in C° (read “Celsius degrees”).
For eg: 20°C is a temperature and 20 C° is a temperature difference.
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Thermal Expansion : SOHAIL ASIF#0341-0345559
Expansion due to increase in temperature. In general, all substances whether
they are in the form of solids, liquids or gases expand on heating except water between 0°C and 4°C
and some aqueous solutions. This is known as thermal expansion.

liquid and gases show only volume expansion where as solid may have all three types of expansions.

Type of thermal expansion

Coefficient of expansion For temperature change ∆ t change in

∆l
(i) Linear α = _________ length ∆l = l0 α ∆t
l0 ∆ t

∆A
(ii) Superficial β = _________ Area ∆A = A0β ∆t
A0 ∆ t

∆V
_________
(iii) Volume γ= volume ∆ V = V0 γ∆t
. V0 ∆t

For all isotropic substances (solids which expand in the same ratio in all directions) α : β : γ = 1:2:3 or γ=3 α ; β =2α; γ =α+ β.
o _ _1
α , β, γ
−

Unit of is C or K

The numerical value of coefficient of linear expansion of a solid depends on the nature of the material
and the scale of temperature used.

5
α per °F= .α per °C.
9

The numerical value of coefficient of linear expansion of a solid is independent of physical dimensions of
the body and also on the unit of length chosen.
The increase in length or linear expansion of a rod depends on nature of material, initial length of rod
and rise of temperature.

The condition required for two rods of different materials to have the difference between the lengths
always constant is L 1α1 =L2 α2 .

A hole in a metal plate expands on heating just like a solid plate of the same size.
A cavity of a solid object expands on heating just like a solid object of the same volume.
If a hollow pipe and a solid rod of same dimensions made of same material are heated to the same rise
in temperature, both expand equally.

A rectangular metal plate contains a circular hole. If it is heated, the size of the hole increases and the
shape of the hole remains circular.
A metal plate contains two holes at a certain distance apart from each other. If the plate is heated, the
distance between the centers of the holes increases.
The change in the volume of a body, when its temperature is raised, does not depend on the cavities inside the body.
Applications of linear expansion :
Platinum (or monel) is used to seal inside glass because both have nearly equal coefficients of linear expansion.
Iron or steel is used for reinforcement in concrete because both have nearly equal coefficients of expansion.
Pyrex glass has low α. Hence combustion tubes and test tubes for hating purpose are made out of it.
Invar steel (steel+nickel) has very low α. So it is used in making pendulum clocks, balancing wheels and
measuring tapes. (Composition of invar steel is 64% steel and 36% nickel).
Thick glass tumbler cracks when hot liquid is poured into it because of unequal expansion.
A brass disc snuggly fits in a hole in a steel plate. To loosen the disc from the hole, the system should be cooled.
To remove a tight metal cap of a glass bottle, it should be warmed.
While laying railway tracks, small gaps are left between adjacent rails to allow for free expansion without
Thermostat is a device which maintains a steady temperature.
Thermostats are used in refrigerators, automatic irons and incubators.
Thermostat is a bimetallic strip made of iron and brass. The principle involved is different materials will
have different coefficients of linear expansion.
When a straight bimetallic strip is heated it bends in such a way that the more expansive metal lies on the outer side.
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ANOMALOUS EXPANSION OF WATER : SOHAIL ASIF#0341-0345559

When water at 0°C is heated, its volume decreases upto 4°C and from 4°C its
volume increases with the increase of temperature. This peculiar behaviour of
water is called anomalous expansion of water. Due to the formation of more
number of hydrogen bonds, water has anomalous expansion.
As the temperature increases from 0°C to 4°C, the density increases and as
the temperature further increases the density decreases. Hence water has maximum
density at 4°C.
Hope’s apparatus is used to demonstrate that water has maximum density at 4°C.
Aquatic animals are surviving in cold countries due to the anomalous expansion of water.
During winter, in cold countries, even if the temperature falls far below 0°C, the water in the frozen lakes
or seas at the bottom remains at 4°C.
When water freezes, it expands and consequently water pipes burst in winter.
When water at 4°C is filled to the brim of a beaker, then it over flows when it is either cooled or heated.

Boyle’s law : At constant temperature, the pressure of a given mass of a gas is inversely proportional to
1
its volume. P α or PV = K (n, T are constant) or P1V1 = P2 V2 . In PV = K, the value of K depends on
V
the mass and temperature of the gas and the system of units.
Boyle’s law can also be defined as follows. At constant temperature, the pressure of a given mass of
gas is directly proportional to its density.
P P P
P α d or = K or 1 = 2 .
d d1 d2

P-V graph at a constant temperature (isothermal) is a rectangular hyperbola.

PV-V graph is a straight line parallel to volume axis.
1
P– graph is a straight line passing through the origin.
V
Many gases obey Boyle’s law only at high temperatures and low pressures.

Charles’ law : At constant pressure, the volume of a given mass of gas increases by 1/273th of its
original volume at 0°C for every 1°C rise in temperature. (or) At constant pressure, the volume of a given
V
mass of gas is directly proportional to the absolute scale of temperature. V α T or = K (at constant P)
T
V-T graph is a straight line passing through the origin.
V-t (in °C) graph is a straight line which when produced meets the temperature axis at –273.15°C or 0 K.

*For 1° rise in temp. Vt = Vo(1 ) V

For 1 0C rise in temperature P t= Po (1 )

o o
-273.15 C tC

Gay Lussac’s law

The pressure of a given mass of gas at constant volume increases by 1/273th of its original pressure
at 0°C for every 1°C rise in temperature. (or) At constant volume, the pressure of a given mass of gas
is directly proportional to absolute scale of temperature. This is also known as
P
. P α T or = K (at constant V)
T
Gas Equation :
Combining Boyle’s law and Charle’s law, the resulting expression is an equation of state for ideal gas.
For unit mass of a gas (1 gram or 1 kg)
PV=rt is called ‘Gas Equation’
PV=mrT (for m grams)
“r” is called gas constant (or) specific gas constant.
The value of “r” depends on nature and mass of the gas.
− 1 K−1. Dimensional formula for “r” is LT 2θ−1 .
S.I. unit of “r” is JKg
− −

For one mole of a gas PV=RT is called universal (or) ideal (or) perfect gas equation.
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The value of R is same for all gases irrespective of their nature.

where n = no. of moles of gas.
S.I. unit of R is J mole − K .
1 −1

1 1
Values of R=8.314 J mole K
−

− −

1 1
R = 0.0821 litre atmosphere mole K
− −

Significance of R:
The value of R does not depend on the mass of gas or its chemical formula.
The fact that R is a constant for all gases is consistent with Avagadro’s hypothesis that “equal
volumes of all gases under same conditions of temperature and pressure contain equal number of molecules”.
Assumptions of Kinetic Theory of Gases

1 All gases consist of molecules which are rigid, elastic spheres identical in all
respect for a given gas.
2. The size of a molecule is negligible as compared with the average distance
between two molecules. The diameter of molecule is about 3 10-10 m.
3. During the random motion, the molecules collide with one another and
with the wall of the vessel.The collisions are almost instantaneous.
4. The molecular density remains uniform throughout the gas. on average
there are 3x1025 molecules/ mole at STP.
5. The collisions are perfectly elastic in nature and there are no forces of
attraction or repulsion between them.
6. Newtonian mechanics is applicable to the motion of molecules.

Pressure
Internal energy of an ideal gas consists of only the K.E of molecules (P.E is absent because there are
no intermolecular forces among the molecules in an ideal or perfect gas).
Internal energy of a real gas consists of P.E and K.E.

Calorimetry:
Calorimetery is the study of the measurement of quantities of heat.
Quantity of heat is the amount of molecular energy stored in a body.
Calorie : The quantity of heat required by one gram of water to raise its temperature from 14.5°C to
15.5°C is called one calorie. 1 calorie=4.186 joule
British Thermal Unit : The amount of heat required by 1 Pound of water to raise its temperature by 1°F is
called one British thermal unit. 1 BTU = 1055 J

Heat Capacity :
The amount of heat required to raise the temperature of the whole body by 1°C is called heat capacity or
thermal capacity. Unitis J/K or Cal/°C.
C = dQ
dT

Heat capacity is an extensive property is depends upon nature as well as amount of substance
Specific heat : The quantity of heat required by one gram of a substance to raise its temperature by 1°C
is called its specific heat.
or
Heat capacity per unit mass. Unit is J/Kg-K or Cal/g-°C.
dQ
c= dQ = c m dT
mdT
Specific heat depends upon the nature of the substance and does not depend upon mass, volume and
heat supplied.
If m is the mass and c is the specific heat of the material of the body, then the thermal capacity = mc cal/°C.

Of all solids and liquids, water has the highest specific heat or specific heat capacity. The value is
1 cal/g/°C or 4200 J/kg/K.

Of all solids, liquids and gases, hydrogen has the highest specific heat. It is equal to 3.5 cal/g/°C.

Specific heat of ice = 0.5 cal/g/°C Specific heat of steam = 0.45 cal/g/°C
Specific heat of a solid at its melting point is infinite.
Specific heat of a liquid at its boiling point is infinite.

The water equivalent of a body is the number of grams of water which require the same amount of heat
as the substance for the same riseof temperature.
If mass is taken in grams then water equivalent is numerically equals to heat capacity
Latent heat (L) is the quantity of heat required by unit mass of a substance to change its state at a
constant temperature. Unit of L is cal/g or J/kg.
Latent heat of fusion is the quantity of heat required by unit mass of a solid to melt it at its melting point.
5
The latent heat of ice is 80 cal/g or 3.35x10 J/kg.
Latent heat of vapourisation is the quantity of heat required by unit mass of a liquid to vapourise it at its boiling point.
6
The latent heat of steam is 540 cal/g or 2.26x10 J/kg.
Latent heat of vapourisation of wate r decreases with the increase of pressure (i.e., increase of boilingpoint).
Latent heat of vapourisation decreaseswith increase in temperature.
Latent heat depends on the nature of a substance and pressure.
During the change of state, the formula used to calculate the heat lost or heat gained is Q = mL.
Steam causes more burns than water at 100°C. The re ason is that steam while condensing to water at
100°C gives out heat at the rate of 540 cal/g.
Steam is used in heat engines as working substance because of its high latent heat.
Heavy water is used as coolant in nuclear reactors because of its high specific heat.
In extinguishing fire hot water is preferred than cold water since hot water becomes vapour quickly and
vapours do not allow fire.
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LAW OF MIXTRUES (OR) CALORIMETRY PRINCIPLE :

If no heat is lost or gained otherwise, the quantity of heat gained by the cold body is equal to the quantity
of heat lost by the hot body. This is called the principle of the method of mixtures.
The principle of method of mixtures is Heat lost = Heat gained.
Calorimeter is generally made up of copper because it has low specific heat and high conductivity and
hence attains the temperature of contents quickly.
To calculate the heat gained or lost when there is no change of state, we use the formula Q=mct.

SPECIFIC HEAT OF GASES :

A gas will have two specific heats.
a) specific heat at constant volume (C V)
b) specific heat at constant pressure (CP)
The value of specific heat may lie between 0 and ∞
In isothermal process, the value of specific heat is ∞ but in adiabatic process its value is zero.

Substances with highest specific heat are bad conductors of heat and with low specific heat are good
thermal and electrical conductors.
The substance with large specific heat warms up slowly and cools down slowly.
CP
CP is greater than C V and =γ
CV
CP CV =R (for 1 mole of gas) where R is universal gas constant R=8.3 J/mol-K
−

FIRST LAW OF THERMODYNAMICS;

Heat given to a system is equal to change in its internal energy plus work done by the system. It is the modified
form of law of conservation of energy.
dQ=dU+dW
sign convention
Heat absorbed into the system is + and released from the system is --
work done by the system when gas expands is + and on the system when gas contracts is --
Increase in internal energy is + and decrease in internal energy is --
A system can exchange its energy with surrounding in two ways
1. By absorbing or releasing heat
2. By performing work
Heat and work both are non state functions
Temperature, pressure,internal energy, entropy,volume are state funtion.
Isothermal Process :
In this process, the pressure and volume of gas changes but temperature remains constant.
The system is in thermal equilibrium with the surroun dings.
It is a slow process.
The internal energy of the system remains constant i.e, du = 0.
It obeys the Boyle’s law i.e., PV=K.

dP
The isothermal elasticity = −

=P.
dV / V
The –ve sign represents, as pressure increases volume decreases.

It takes place in a conducting vessel.

Adiabatic Process :
The pressure, volume and temperature of a gas change but total heat remains constant. i.e., dQ=0
(Q=constant)
It is a quick process. PVγ=constant
The internal energy changes as temperature changes. The adiabatic elasticity of gas is γP.
The adiabatic process is represented by the equations It takes place in a non conducting vessel.

Quantity
Quantity
Sl. Name of the which
. Result
remains
No process becomes in I law
constant
zero

1. Isothermal temperature dU dQ=dW

2. Isobaric pressure None dQ=dU+dW

3. Isochoric volume dW dQ=dU

4. Adiabatic heat energy dQ dU= dW

−

Adiabatic expansion causes cooling and contraction causes heating.

Isochoric process : It is a process in which the volume of the system remains constant.
i.e., ΔV=0 for such process ΔW=0.
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Isobaric process : It is a process in which the pressure of the system remains constant.
i.e., ΔP=0.
The equation of state for different types of processes :
For given amount of heat work done is maximum for isothermal process.
During expansion of a gas between same initial and final volume work done is max. for isobaric
>isothermal > adiabatic
During contraction of a gas between same initial and final volume work adiabatic > isothermal > isobaric
HEAT ENGINES :
Heat engine is a device used to convert heat into mechanical work.
Heat engines are of two types namely internal combustion engine and
external combustion engine. Source at T1
a) Internal combustion engine is an engine in which heat is produced in Q1
the engine itself. Working substance

Ex : Otto engine and Diesel engine.

Q2
b) In external combustion engine, heat is produced outside the engine.
Sink at T2
Ex : steam engine.
Heat engine absorbs a quantity of heat Q 1 from a source, performs an amount of work W, and returns to
the initial state after rejecting some heat Q2 to a sink. The working substance, which is a gas or liquid
undergoes a cyclic thermodynamic process. The source is at a higher temperature than the sink.
The efficiency η of a heat engine is given by
heat converted to work
η= =
total heat absorbed

= 1− 2 =1
W Q −Q Q2
−

.
Q1 Q1 Q1
From the above expression it is clear that the efficienty of a heat is always less than 1 or 100%.

SECOND LAW OF THERMODYNAMICS :

(a) Classius statement : It is impossible for a self acting machine. (The machine which does not
require any external source of energy for working), unaided by any external agency to transfer heat
from a body at lower temperature to another at a higher temperature. (or)
Heat cannot of itself flow from a colder body to a hotter body.
(b) Kelvin statement : It is impossible to construct a heat engine operating in a cycle to convert the
heat energy completely into work without any change of working substance. (or)
No heat engine can convert whole of the heat energy supplied to it into useful work.

Reversible process
A reversible process is one which can be retraced in exactly reverse order, without producing
any changes in the surroundings. The system always remains close to equilibrium. In the rev-
erse process thermal and mechanical effects at each stage are exactly reversed, the working
substance is restored to original conditions. No process is 100% reversible but process of
liquefaction and evaporation, slow compression of gas in cylinder, electrolysis etc are nearly
almost reversible. Carnot cycle is a reversible cycle.
All changes which occur suddenly or which involves any sought of friction, internal resistance,
viscosity, inelasticity are irreversible. ex explosion, most of chemical reactions.
Carnot Engine : Carnot developed, ideal heat engine that has maximum possible efficiency consistent
with the second law. The working substance is imagined to go through a cycle of four processes known

Carnot heat engine essentially consists of four components. They are

i) a cylinder with perfect thermal insulating walls, perfect conducting P
A(P 1V1 )
base and a tight fitting perfect insulating and frictionless piston (It I (T1 ) B(P 2V2)
consists of a working substance). IV II

ii) a hot body of infinitely large heat capacity at a constant temperature D(P4V4 ) C(P3 V3)
. III (T 2)
serving as a source. V

iii) a cold body of infinitely large heat capacity at a constant temperature serving as a sink and
iv) a perfectly thermal insulating stand.

The working substance, an ideal gas, undergoes a cycle which consists of two
.

isothermal and two adiabatic processes as follows.

i) Step I (AB) : The gas expands isothermally at source temperature T 1 and absorbs heat Q1
ii) Step II (BC) : The gas expands adiabatically until its temperature decreases to the sink temperature T2
 8
iii) Step III(CD) : The gas is compressed isothermally at T2 , rejecting heat Q2.

iv) Step IV(DA) : The gas is compressed adiabatically until it returns to its initial state A.

v) All the steps are carried out very slowly so that there are no dissipative effects.
−

vi) The process is reversible.

vii) W = Q1 – Q2 .

Q1 T1 T2
viii) = It can be shown that the efficiency of Carnot engine is η = 1
Q2 T2
−

T1
η can be 100% only if T2 = 0. i.e., the sink is maintained at absolute zero which is impossible.
A decreases in T2 is more effective than an equal increase in T 1 in increasing the efficiency.
The efficiency of engine depends upon the temperature of source and sink.
The efficiency of the engines working between same source and sink is same.
The efficiency of a reversible engine is independent of the nature of the working substance.
The net external work done obtained is the area enclosed.
Carnot theorem : No engine working between two given temperatures can be more efficient than a
reversible engine working between the same two temperatures have the same efficiency, whatever may
be the working substance.
The Carnot’s cycle working in the opposite direction can perform the following two functions.
i) It can further coot the colder body. ii) It can further heat the hot body.
a) When reversed heat engine is used to further cool the colder system the arrangement is called a
refrigerator .

b) When the reversed heat engine is used to further heat the hotter system it is known as Heat pump .

Principle of Refrigerator :
a) It will absorb an amount of heat Q 2 from the sink (contents of refrigerator) at lower temperature T2.

b) As heat is to be removed from the sink at lower temperature, an amount of work equal to Q1 – Q 2 is
performed by the compressor of refrigerator and then it rejects the total heat Q to the same
(atmosphere) through the radiator fixed at its back.
Coefficient of performance :
The ratio of the quantity of heat removed per cycle from the contents of the refrigerator to the work done
by the external agency to remove it is called co-efficient of performance of the refrigerator. It is
denoted by ‘β’.
Q2 Q2 Q1 T T2
β= = But = 1 ∴ β=
w Q1 Q2 −
Q2 T2 T1 −
−

T2
ENRROPY:
If a system absorbs or releases heat during a reversible process then the change in entropy is defined as

⌬Q ⌬Q
⌬S ⫽ (For Isothemal) ⌬ S⫽ ( If temp changes)
T Tav
If a process occurs in aclosed system, the entropy of the system increases
for irre-versible processes and remains constant for reversible processes. It never decreases .

⌬ S ⱖ 0 (second law of thermodynamics) ,

In carnot engine, all processes are reversible and no wasteful energy transfers occurs due to friction. Carnot
cycle is a reversible cycle. But because it has to absorb heat during isothermal expansion its entropy increases
to complete the cycle system has to decrease entropy. As stated above No close system can decrease its
entropy so it has to lose heat to decrease entropy, so even cornot engine is not 100% efficient.
If a reversible process loses heat at the same temprature at which it has gained it has to lose an equl amount of heat
to make zero change in entropy over its complete cycle, but in this way no work is performed because
all the heat goes to cold body. Therefore an efficient engine should have its cold body at a temperature
as low as possible so that it release lessheat to it to decrease its entropy and to complete the cycle
.

Coefficient of thermal conductivity :

In steady state, the amount of heat Q transmitted through a conductor is directly proportional to
i) the temperature difference between the faces (T2 T 1)°C. −

ii) the area of the cross-section of the slab A.

iii) the time of the flow of heat t.
iv) inversely proportional to the di stances between the two faces “d”.
A(T1 T 2 )t KA (T1 T 2 ) t
Qα
−

Q= ;
d d
Where K is a constant that depends upon the nature of the material of the rod and is known as
coefficient of thermal conductivity .

Coefficient of thermal conductivity is defined as the quantity of heat flowing per second across a cube of
1 1
unit edge when its opposite faces have a temperature difference of 1°C. Unit of K is cal/cm/s/°C or Wm K
−