10/23/2021

Thermodynamic Processes
When a thermodynamic system changes from one state to another, the operation is called a
Process. These processes involve the change of conditions (temperature, pressure and volume). The
various types of thermodynamic processes are:
(1) Isothermal Processes: Those processes in which the temperature remains fixed, are termed
isothermal processes. This is often achieved by placing the system in a thermostat (a constant
temperature bath).
For an isothermal process dT = 0
(2) Adiabatic Processes: Those processes in which no heat can flow into or out of the system, are
called adiabatic processes. Adiabatic conditions can be approached by carrying the process in an
insulated container such as ‘thermos’ bottle. High vacuum and highly polished surfaces help to
achieve thermal insulation.
For an adiabatic process dq = 0

(3) Isobaric Processes: Those processes which take place at constant pressure are called
isobaric processes. For example, heating of water to its boiling point and its vaporization take
place at the same atmospheric pressure. These changes are, therefore, designated as isobaric
processes and are said to take place isobarically.
For an isobaric process dp = 0

1
 10/23/2021

(4) Isochoric Processes: Those processes in which the volume remains constant are
known as isochoric processes. The heating of a substance in a non-expanding chamber is
an example of isochoric process.
For isochoric processes dV = 0.
(5) Cyclic Process: When a system in a given state goes through a number of different
processes and finally returns to its initial state, the overall process is called a cycle or
cyclic process.
For a cyclic process dE = 0, dH = 0.

2
 10/23/2021

Reversible and Irreversible Processes

A thermodynamic reverse process is one that takes place infinitesimally slowly and its
direction at any point can be reversed by an infinitesimal change in the state of the system.

Figure 6: (a) Reversible expansion occurs by decreasing the pressure on the piston by infinitesimal amount. (b)
Irreversible expansion occurs by sudden decrease of pressure from P to P- , when the gas expands rapidly in a
single operation.

In fact, a reversible process is considered to proceed from the initial state to the final state through an
infinite series of infinitesimally small stages. At the initial, final and all intermediate stages, the
system is in equilibrium state. This is so because an infinitesimal change in the state of the system at
each intermediate step is negligible. When a process goes from the initial to the final state in a single
step and cannot be carried in the reverse order, it is said to be an irreversible process. Here the
system is in equilibrium state in the beginning and at the end, but not at points in between. Consider
a certain quantity of a gas contained in a cylinder having a weightless and frictionless piston. The
expansion of the gas can be carried by two methods illustrated in Fig. 6. Let the pressure applied to
the piston be P and this is equal to the internal pressure of the gas. Since the external and internal
pressures are exactly counterbalanced, the piston remains stationary and there is no change in
volume of the gas. Now suppose the pressure on the piston is decreased by an infinitesimal amount
dP.

3
 10/23/2021

Thus the external pressure on the piston being P – dP , the piston moves up and the gas will
expand by an infinitesimal small amount. The gas will, therefore, be expanded infinitely
slowly i.e., by a thermodynamically reversible process. At all stages in the expansion of the
gas, dP being negligibly small the gas is maintained in a state of equilibrium throughout. If at
any point of the process the pressure is increased by dP, the gas would contract reversibly.
On the other hand, the expansion is irreversible (Fig. 6 b) if the pressure on the piston is
decreased suddenly. It moves upward rapidly in a single operation. The gas is in equilibrium
state in the initial and final stages only. The expansion of the gas, in this case, takes place in
an irreversible manner.

4
 10/23/2021

Calorimetry
When a body is heated, its temperature rises. If 100g of copper and 100g of water are heated
by similar burners for the same time, the rise in temperature is not the same in the two cases.
The rise in temperature depends on the quantity of heat given to the body and the nature of
its material. Let H be the quantity of heat given to a body of mass m and let the rise in
temperature be T. Then, H = mcΔT where C is a constant that depends upon the nature of the
substance. C is called the specific heat of the substance.
Calorie: It is the quantity of heat required to raise the of one gram of water from 14.5°C to
15.5°C. This is the standard unit recommended by International Committee of Pure Physics.
For ordinary purposes, the specific heat of water is taken as 1 but specific beat of water is
not 1 at all temperatures. For practical purposes Calorie may be defined as the amount of
heat required to raise the temperature of 1 gram of water through 1°C.

5
 10/23/2021

Specific Heat: It is defined as the quantity of heat required to raise the

temperature of unit mass of a substance through one degree.
C=H/mΔT
In SI system, the unit of H is in Joules, m is in kg and T is in K. Therefore the
unit of specific heat will be J/kgK.

Thermal Capacity: It is the quantity of heat required to raise the temperature of the whole of
the substance through 1°C.
Thermal capacity= m.c.1
= m.c j/k

Example: A 500 g cube of lead is heated from 25 °C to 75 °C. How much energy in (J)
was required to heat the lead? The specific heat of lead is 0.129 J/g.°C.

C=H/mΔT
H= C. m. ΔT
= C. m. (Tfinal-Tinitial)
= 0.129 J/g .°C * 500g* (75-25)
= 3225 J

6
 10/23/2021

Example: A 25g metal ball is heated 200 °C with 2330 Joules of energy. What
is the specific heat of the metal?

C=H/mΔT
= 2330J/25 *200
= 0.466 J/g. °C

Regnault's Method of Mixtures

Specific Heat of Solids: Regnault was the first to devise the apparatus commonly used in the
laboratories to find the specific heat of a solid or liquid employing the method of mixtures.
Copper Block Calorimeter
The Nernst and Lindemann designed a calorimeter called the copper block calorimeter. It
consists of a Dewar flask A having a copper block C fixed inside it. T, T arc the terminals of
the leads of the thermocouple to measure the temperature of the block C. The flask is
covered from outside to prevent any loss of heat to the surroundings. Through the tube B, a
hot solid can be dropped Fig. 3.1

7
 10/23/2021

The substance whose specific heat is to be determined is heated to a known high temperature
and then gently dropped through the tube B into the block C. The copper block has high
thermal conductivity and a uniform final temperature is reached in a short time. The
temperature is measured with the help of a calibrated thermocouple, the copper block C
acting as the hot end. To avoid air currents the tube B is closed with an automatic electrical
arrangement after the substance has been dropped into the block C. The whole apparatus can
be maintained at a desired temperature. From the heat gained by copper block kind the heat
lost by the substance, the specific heat of the substance can be calculated.

8
 10/23/2021

Newton's Law of Cooling

Newton's Law of Cooling states that the rate of loss of heat of a body is directly proportional
to the difference of temperature of the body and the surroundings. The law holds good only
for small difference of temperature. Also, the loss of heat by radiation depends upon the
nature of the surface of the body and the area of the exposed surface.
dH dH
∝ (T-T0) ⇒ − = k(T − To)
dt dt

dH= mcdT
d𝐻 𝑑𝑇
Therefore rate of loss of heat: = 𝑚 𝑐 𝑑𝑡 … . 1
𝑑𝑡

From newtons law of cooling

dH
− dt = k(T − To) ….(2)

K= thermal conductivity constant depend upon the area and the nature of the surface of the
body. From eq. 1 and 2

𝑑𝑇
−𝑚 𝑐 = k (T − T0)
𝑑𝑡
d𝑡 𝑘
= − mc dt = - k dt ….. (3)
𝑇−𝑇0

Therefore log (T-T0)= -Kt + C ……(4)

If a graph is plotted between t and log (T-To) it is a straight line
T0 = temperature of the surrounding

9
 10/23/2021

Log (T-T0)

Time (t)

Specific Heat of a Liquid :

A and B are two identical calorimeters containing equal volumes of hot water
and the hot liquid respectively. The two calorimeters are made of the same
material and their outer surfaces are equally polished. The calorimeters are kept
inside a constant temperature enclosure. The thermometers T1 and T2 measure
the temperature of water and liquid Fig. 3.3 (ii). The temperature of the two
calorimeters arc noted after regular intervals of time (say one minute). Graphs
are plotted between temperature and time, for water and the liquid Fig. 3.4.

10
 10/23/2021

From eq. (III)

ⅆ𝑡 𝑘
න = නⅆ𝑡
𝑇 − 𝑇0 𝑚𝑐

In the case of water, suppose

Mass of water = m
Water equivalent of the calorimeter A= w
Time taken by water to cool from 60 °C to 55 °C = t1
55
d𝑇 𝑘
න = − (𝑚+𝑤) . 𝑡1 (IV)
𝑇−𝑇0
60

11
 10/23/2021

Suppose mass of liquid = M

Water equivalent of the calorimeter B= w
Specific heat of liquid = C
Time taken by liquid to cool from 60 °C to 55 °C = t2

55
ⅆ𝑇 𝑘
න =− .𝑡
𝑇 − 𝑇0 (MC + 𝑤) 2 (V)
60

From eq. (IV) and (IV)

𝑀𝐶 + 𝑤 (m + w)
=
𝑡2 𝑡1
𝑚+𝑤 𝑡2 𝑤
C=− −𝑀 (𝑉𝐼)
M 𝑡1

12
 10/23/2021

Example 1: A liquid takes 5 minutes to cool from 80°C to 50°C. Now much
time will it take to cool from 60°C to 30°C? The temperature of the surrounding
is 20°C.
We have ⅆ𝑡
න = −𝑘 නⅆ𝑡
𝑇 − 𝑇0
T0= 20 °C
In the first case, 50
ⅆ𝑇
න = −k ∗ 5
𝑇 − 𝑇0
80 50
Log [T-T0] = 5k
80
Log[50-20/80-20]=-5k
Log 30/60=-5k
Log 60/30= 5k eq.1

In the second case, suppose the time taken is t minutes,

30
𝑇
න = −k
𝑇 − 𝑇0
60
Log [30-20/60-20]= −kt
Log 10/40=-kt
Log 40/10= kt eq. 2 Log 60/30= 5k eq.1

Dividing eq. 2 by 1
t/5=log4/log2=2
T= 10minutes

13
 10/23/2021

Example 2: Equal volumes of water (density 1 g/cm3) and alcohol (density 0.8
g/cm3) when put in similar calorimeters lake 100 seconds and 74 seconds
respectively to cool from 50°C to 40°C Calculate the specific heat of alcohol.
Thermal capacity of each calorimeter is numerically equal to the volume of
either liquid.

14
 10/23/2021

Example 4: A liquid fakes 4 minutes to wolfram 70°C to 60°C. How much time
will it take to cool from 50°C to 40°C? The temperature of the surroundings is
25°C. Newton's law of cooling is applicable throughout the process.

Specific Heat of A Liquid—joules Electrical Method

The apparatus consists of a calorimeter in which a heater coil (wire) of resistance R is
enclosed. The two ends of the wire are connected to the terminals on the lid. The
calorimeter is enclosed in a wooden box. The wire R is connected in series with a battery, a
key, a rheostat and an ammeter. A voltmeter is connected parallel to the wire (Fig. 3.5).
The liquid whose specific heat is to be determined is taken in the calorimeter. Current is
passed through the wire for a known interval of time. The rise in temperature of the
calorimeter and the liquid is noted with the help of a thermometer. The current is passed for
such a time that the rise in temperature is about 10°C.
Suppose, the mass of the liquid is M, specific heat of the liquid is C and water equivalent of
the calorimeter is w.
Initial temperature of the liquid = T1°C

15
 10/23/2021

Final temperature of the liquid = T20C

P.D. across the wire = E volts P.D.= potential difference
Current flowing = I amperes
Time = (seconds
Heat produced = E.I.t / 4 2 calories
Heat gained by the liquid and the calorimeter
= (MC + w) (T2— T1)
(MC + w) + (T2— T1) = E.I.t /4.2
C = E.I.t / 4.2 (T2 — T1) = w/ M

16