Heat & Thermodynamics

Definition of Heat : Heat is energy in transit which is transferred from one body to the other,
due to difference in temperature, without any mechanical work involved.

THERMAL EXPANSION:
Expansion due to increase in temperature.
Important facts : In every type of expansion, the increase in dimension is observed to be proportional to the
original dimension and the rise in temperature.
Solids are made up of atoms and molecules. At a given temperature, the atoms and molecules
are located at some equilibrium distance. When heat is added to a solid. The amplitude of
vibrations of atoms and molecules increase. Due to this, inter-atomic separation increases, which
results in the expansion of solids.
Cause of thermal expansion : Molecules are held together by elastic forces and they vibrates
with some constant mean distance between them.
As temperature increases, vibration energy of the constituent particles increases which results in
increase in separation between the particles and hence there is thermal expansion.

TYPE OF THERMAL EXPANSION:

(1) Linear expansion
Suppose the solid in the form of rod of length Lo is heated, till its temperature rise to T. If the
length of the rod becomes L (say), then it is found that increase in length ( L Lo) is
(a) directly proportional to its original length ( L Lo) Lo
(b) directly proportional to rise in temperature of rod i.e. ( L Lo) T
From (a) and (b)
( L Lo) Lo T
change in length L = L Lo = Lo T
( where is co-efficient of linear expansion)

L = Lo + LoT
L = Lo (1 + T )
( Lo is initial length of the rod , where is co-efficient of linear expansion)
Definition of Coefficient of linear expansion
It is defined as the change in length per unit original length per unit change in its temperature.
Note : It may be pointed out that value of coefficient of liner expansion of solid rod does not
depend upon the shape of the cross-section of the rod.

(2) Superficial expansion

Superficial Expansion : When a solid is heated its surface area and volume as well as its linear
dimensions will increase. Increase of area is spoken of as superficial expansion .
Let Ao = initial surface area of solid
A = surface area of solid when temperature changed by T , then
Change in surface area i.e. (A Ao)
(a) will directly proportional to Ao
(b) will directly proportional to T
From (a) and (b)
A Ao Ao T
change in Area A = A Ao = Ao T
(where is co-efficient of superficial expansion)
A = Ao + Ao T
A = Ao ( 1 + Ao T )
( Ao is initial area of the rod, where is co-efficient of superficial expansion)
Definition of Coefficient of superficial expansion:
It is defined as the change in surface area per unit surface area per unit change in its temperature.

(3) Volume expansion

Let Vo = initial Volume of solid
V = Volume of solid when temperature changed by T , then
Change in Volume i.e. (V Vo)
(a) will directly proportional to Vo
(b) will directly proportional to T
From (a) and (b)
(V Vo) Vo T
change in volume expansion V = V Vo = Vo T
(where is co-efficient of volume expansion)
V = Vo + Vo T
V = Vo ( 1 + Vo T )
( Vo is initial volume of the rod, where is co-efficient of volume expansion)
(1) For isotropic solid , 1 = 2= 3= (say). So = 2 and = 3
(2) For anisotropic solids , = 1 + 2 and = 1 + 2 + 3
Here 1 , 2 and 3 are coefficient of linear expansion in X , Y and Z directions respectively.
Example : A copper and a tungsten plate having a thickness = 2mm each are riveted together
so that at 0C they form a flat bimetallic plate. Find the average radius of curvature of this plate
at T = 200C. The coefficients of linear expansion for copper and tungsten are and c = 1.7 x 10-5
K-1 and t = 0.4 x 10-5 K-1
Solution :

Lo(1 + 1T) = (R + /2) .. (1)

Lo(1 + 2T) = (R /2) . (2)
From (1) and (2), we get
RT (1 2) = + [ T/2 ](1 + 2)
RT (1 2)

Variation in Density with temperature

Variation of density of Solids and liquids with temperature

When a given mass of a solid or liquid is heated, its volume increases. Accordingly, the density
of a solid or a liquid decreases on heating.
Let Vo and V be the volumes of a solid (or liquid) at Temperature T and T + T respectively. If
is its coefficient of cubical expansion, Then
V = Vo ( 1 + Vo T ) .(i)
Let o and be the densities of the solid or liquid at temperature T and T + T . If the mass of the
liquid or solid is M
Then o = M/Vo and = M/V
Substituting for Vo and V in equation (i), we have
M/ = M/o (1+ T )
or = o /(1+ T )
= o (1+ T )1
Expanding by binomial theorem and neglecting terms containing higher powers of T , we
have
= o (1 T )
With increase in temperature, volume increases, so density decreases and vice-versa.

Note:
(i) for liquids are in order of 10-3
(ii) For water, density increases from 0 to 4C so is ve (0 to 4C) and for 4C to higher
temperature is +ve . At 4C density is maximum.
Example : A sphere of diameter 7cm and mass 266.5 gm floats in a bath of liquid. As the
temperature is raised, the sphere just begins to sink at a temperature of 35C. If the density of the
liquid at 0C is , find the co-efficient of cubical expansion of the liquid. Neglect the expansion of
the sphere.
Solution : The sphere will sink in the liquid at 35C, when its density becomes equal to the
density of liquid at 35C.

The density of sphere , s=

( density of sphere is constant)
35= 1.483 gm/cm3
Now ,
0 = 35[1 + ]
1.527 =1.483[1 + x 35]
1.029 = 1 + x 35
= 0.00083 / C
( density of sphere is constant)
Apparent expansion of liquid in a Container

Expansion of Liquids
As liquids have no definite shape, the liner and superficial coefficient cannot be studied. Further,
for heating it has to be kept in a container. Obviously when the liquid is heated, the container will
also expand.

The observed expansion of liquid is called apparent expansion and it is different from real
expansion of the liquid.
Initially container was completely filled with liquid. Temperature is increased by t
Final volume of liquid VL = Vo(1 + LT )
Final volume of container VC = Vo(1 + CT )
So, overflow volume of liquid relative to container V = VL VC
V = Vo( L C)T
So coefficient of apparent expansion of liquid w.r.t. container
apparent = L C
EXPANSION IN ENCLOSED VOLUME:

Increase in height of liquid level in tube when bulb was initially completely filled :

Initially

Finally

A sphere of metal A(1) just inside a spherical shell of metal B(2) at any temperature T. If the
temperature of metals is increased and 1 > 2 then volume stress will be developed (compressive
in metal A and tensile in metal B).
But if(1 < 2) the free space will be created between metals.

With same amount of change in temp. the expansion of radius will be same
R = Ro(1 + T )

Example : A one litre glass flask contains some mercury. It is found that at different temperature
the volume of air inside the flask remains the same. What is the volume of mercury in this flask
if coefficient of linear expansion of glass is while volume expansion of mercury is 1.8 x 10-4
/C ?
Solution: If V is the volume of flask, VL of mercury and VA of air in it,
V = VL + VA
Now as with change in temperature volume of air remains constant, the expansion of mercury
will be equal to that of the whole flask i.e.,
V = VL
VG = VLL
[ As , V = V ]
Here V = 1 litre = 1000 cc and G = 3 G = 27 x 10-6 / C
VL = (1000 x 27 x10-6 /1.8 x 10-4 / )= 150 cc.

THERMAL STRESS

A rod of length clamped between two fixed walls

For change in temperature

Energy stored in rod E = (1/2) stress strain volume

For increase in temperature stress will be compressive and for decrease in temperatue stress will
be tensile .
Illustration: Two metal rods of the same length and area of cross-section, are fixed end to end
between rigid supports. The materials of the rods have Young modulus Y1 and Y2 , and
coefficients of linear expansion 1 and 2 . For what condition the junction between the rods does
not shift if the rods are cooled.
Solution : Tension must be the same in both the rod for their junction to be in equilibrium.
Y1A 1T = Y2A2T
Illustration : When the temperature of a body increases from T to T + T, its moment of inertia
increases from I to I + I. The coefficient of linear expansion of the body is . Find the ratio of
I/I
Solution : I = mr2
I + I = m[r(1 + T)]2

or I + I = [mr2(1 + 2 T)] = I(1 + 2 T)

or I/I = 2 T
Effect of Temperature on Pendulum Clocks

Variation Of Time Period Of Pendulum Clocks :

(by using Binomial expansion)

Where , T = increase in time period

Illustration : A pendulum clock with a pendulum made of Invar has a period of 0.5 s and is
accurate at 25 C. If the clock is used in a country where the temperature averages 35 C, what
correction is necessary at the end of a month (30 days) to the time given by the clock?
Solution: In time interval , the clock will become slow (or will lose time) by

So,

Volume Coefficient & Pressure coefficient of gases

Volume Coefficient :

Consider a given mass of a gas is heated through 1 C at constant pressure. Now the ratio of the
increase in volume to the original volume at 0 C is defined as volume coefficient.
If VT and V0 be the volumes of a given mass of gas T C and 0 C respectively, then

Pressure coefficient :

Consider a given mass of a gas is heated through 1 C at constant volume Now the ratio of the
increase in pressure to the original pressure at 0 C is defined as the pressure coefficient. If PT
and P0be the pressures of a given mass of a gas at T C and 0C respectively, then

where p is known as pressure coefficient.

CALORIMETRY
Calorie:

The amount of heat needed to increase the temperature of 1 gm of water from 14.5C to 15.5C
at STP is known as 1 calorie
Specific Heat:

It is heat required to raise temperature by 1 C or 1 K for unit mass of the body.

(be careful about unit of temperature, use units according to the given units of c)
Latent Heat:

The amount of heat required to change one phase of 1 gm of a substance to another phase.
Q = mL

L = latent heat of substance in cal/gm or in Kcal/kg.

Lice = 80 cal/gm Specific latent heat of fusion of ice
Lsteam = 540 cal/gm Specific latent heat of vaporization of water
Molar Heat Capacity:

If instead of unit mass we consider one mole of a substance, the heat required to change the
temperature of one mole of a substance through 1C (or K) is called molar heat capacity or molar
specific heat and is represented by C.
If the molecular weight of a substance is M :

Its SI units are (J/mol K)

Thermal-capacity :

If instead of unit mass we consider the whole body, (of mass m), the heat required to raise the
temperature of a given body by 1C is called its thermal capacity , i.e.,
Thermal capacity
Thermal capacity of a body depends on the mass and nature of body. It has units (J/K) or cal/C
Water-Equivalent :

If thermal capacity of a body is expressed in terms of mass of water it is called water-equivalent

of the body,
i.e., water-equivalent of a body is the mass of water which when given same amount of heat as to
the body, changes the temperature of water through same range as that of the body, i.e.,

[where : W = mass of water ; m = mass of substance ]

The unit of water equivalent W is g while its dimension [M].

Principle of Calorimetry

When two bodies (one being solid and other liquid or both being liquid) at different temperature
are mixed, heat will be transferred from body at higher temperature to a body at lower
temperature till both acquire same temperature.
The body at higher temperature releases heat while body at lower temperature absorbs it, so that :
Heat lost = Heat gained

i.e. principle of calorimetry represents the law of conservation of heat energy.

Illuatration : The temperature of equal massesof three different liquids A, B and are 12C, 19
C and 28 C respectively. The temperature when and are mixed is 16 C and when and are mixed
is 23 C. What would be the temperature when and are mixed?
Solution: In accordance with principle of calorimetry :
When A and B are mixed
m CA (16 12) = m CB (19 16)
=> CA = (3/4)CB
and when B and C are mixed
m CB (23 19) = m CC (28 23)
CC = (4/5)CB
Now when A and C are mixed if T is the common temperature of mixture:
m CA (T 12) = m CC (28 T)
Substituting CA and Cc from above,
(3/4)(T 12) = (4/5)(28 T)
which on solving gives,
T = 20.25 C

Illustration : A solid material is supplied heat at a constant rate. The temperature of the material
is changing with the heat input as shown in figure. Study the graph carefully and answer the
following questions :

(i) What do the horizontal regions AB and CD represent?

(ii) If CD = 2 BA , what do you infer?
(iii) What does slope DE represent?
(iv) The slope of OA > the slope of BC .What does this indicate ?
LAWS OF THERMODYNAMICS
Zeroth Law of Thermodynamics:

If two bodies A and B are in thermal equilibrium and A and C are also in thermal equilibrium,
then B and C are also in thermal equilibrium.
Prevost Theory of Exchanges:

According to this theory, every body is continuously emitting radiant energy in all directions at a
rate depending only on the nature of its surface and its temperature and it is absorbing radiant
energy from all surrounding bodies at a rate depending on its surface and the temperature of the
surrounding bodies.
Mechanical Equivalent of Heat:

Whenever mechanical work is transformed into heat or heat into mechanical work, there is a
constant ratio between the work and the amount of heat. This ratio is called mechanical
equivalent of heat and is denoted by J .
Thus, if W be the amount of work done and Q the amount of heat prouduced, we have
W/Q = J ,

=> W = JQ
If Q = 1 unit then J = W . Therefore, J is numerically equal to the mechanical work required to
produce one unit of heat.
First law of Thermodynamics :

It is the consequence of conservation of energy for gaseous system.

Heat supplied to the gas = Increase in internal energy + work done by the gas.
Q = U + W

Q = + ve

=> heat is supplied to the gas

in differential form dQ = dU + dW = ve
=> heat is taken out from the gas
and dQ = nCdT

C = molar specific heat

C = Cp (constant pressure);

C = Cv =(constant volume)

Degree of Freedom (f)

NUMBER OF INDEPENDENT MOTION OF THE PARTICLE IS EQUAL TO ITS

DEGREE OF FREEDOM.
For monoatomic gases ; f = 3
For diatomic gases ; f = 5
For triatomic non linear gases : f = 6
Internal Energy :

Root mean square velocity of a particle of mass m

Internal energy U = KE + PE (PE = 0 for ideal gas)

Due to translational mode

 For one mole U = (3/2)RT

Therefore energy corresponding to one degree of freedom = RT/2 (from law of equipartion of
energy)
If degree of freedom is f then,
U = fRT/2
For n mole

dU = (f/2)nRdT
dU = +ve for increase in temperature
dU = ve for decreases in temperature

(P = pressure of the gas of which work is to be calculated)

W = + ve for work done by gas (in expansion of gas)
W = ve for work done on the gas (in contraction of gas)
Mayors Relation
Cp C v = R

Note: C of a gas depends on the process of that gas, (which is infinite in Isothermal Process).
Ratio of specific heat of gasses :

And

Indicator Diagram:

This is graph between pressure and volume of a system under going operation,

(1) Every point of Indicator Diagram represents a unique state (P, V, T) of gases.
(2) Every curve on Indicator Diagram represents a unique process.
Isochoric & Isobaric Process
Isochoric Process (V = constant)

dV = 0
=> dW = 0

By First Law of Thermodynamic

dQ = dU = n Cv dT

Isobaric Process (P = constant)

dP = 0
By First Law of Thermodynamics
dQ = dU + dW

where dW = n R (T2-T1 )
* Be careful if V = 0 then not necessarily an Isochoric Process.
* If P = 0 then not necessarily an Isobaric Process
Isothermal Process
Isothermal Process (T = constant):

dU = 0

( dT = 0 )

PV = K
By First Law of Thermodynamics
dQ = dW
dQ = P dV

Adiabatic Process

dQ = 0 but if Q = 0 , it is not necessarily adiabatic.

dW = -dU By First Law of Thermodynamics

How to get the process Equation for adiabatic

(i) First Law of Thermodynamics with process condition

(ii) Differential form of gas law

d(PV) = d(nRT)
PdV = n R dT

P dV + V dP = -(-1)PdV
V dP = -(PdV)

lnP = -lnV + lnC

PV = constant

TV-1 = constant
TP1-= constant
For Adiabatic Process PV = constant

Slope of adiabatic curve is more in magnitude in comparison to the slope of the isothermal curve.
Bulk Modulus of Gases:

Isothermal bulk modulus of Elasticity

Adiabatic bulk modulus of Elasticity