CHAPTER 7:

THERMODYNAMICS
What is thermodynamic process?

When the system undergoes change

from one thermodynamic state to final
state due changes in properties like
temperature, pressure, volume etc, the
system is said to have undergone
thermodynamic process
Heat is a transfer of energy due to a difference of
temperature.

System:

Work is a transfer of energy by mechanical

means (NOT due to temperature difference).

Any object or set of objects that we wish to

consider.

Anything else in the universe, refer as

environment or surroundings
THE THERMAL EQUILIBRIUM

THE THERMAL EQUILIBRIUM:

“Two objects placed in thermal contact, they

will eventually come to the same temperature.
When they do, we say they are in thermal
equilibrium”.
Two objects are defined to be in thermal
equilibrium if, when placed in thermal contact,
no energy flows from one to other and their
temperature don‟t change.
 INTERNAL ENERGY

We defined the internal energy of a system as the

sum total of all the energy of the molecules of the
system.

The internal energy of a system would increased if

work was done on the system OR heat is were added
to it.

Similarly, the internal energy would be decreased if

heat flowed out of the system OR if work were done
by the system.
LAWS of THERMODYNAMICS

1.The Zeroth Law of Thermodynamics

2.The First Law of Thermodynamics
3.The Second Law of Thermodynamics
4.The Third Law of Thermodynamics

1.The Zeroth Law of Thermodynamics

definition: two systems are in thermal

equilibrium if there is no net flow of heat
between them and they brought into thermal
contact.
The First Law of Thermodynamics:
The First Law of Thermodynamics:

The First Law of Thermodynamics:

“The change in internal energy of a closed system

will be equal to the energy added to the system
minus the work done by the system on its
surroundings”.

This is the law of conservation of energy, written in a

form useful to systems involving heat transfer.
 Sign Convention

1) HEAT : Q (+) : when the system gain heat

Q (-) : when the system loses heat

1) 2) WORK : W (+) : when it is done by the

system
W (-) : when it is done on the
system
EXAMPLE: 1
2500 J of heat is added to a system, and 1800 J of
work is done on the system. What is the change
internal energy of the system? Ans: 4300 J
EXAMPLE 2
The figure shows a system and its surroundings. In part (a) the
system gains 1500 J of heat from its surroundings, and 2200 J of
work is done by the system on the surroundings. Determine the
change in the internal energy of the system. Ans: -700J

(b) the system also gains 1500 J of heat, but 2200 J of work is done
on the system by surroundings. Determine the change in the
internal energy of the system. Ans: +3700 J
THERMAL PROCESS IN THE
FIRST LAW of
THERMODYNAMICS
4 common thermal processes:
1. ISOTHERMAL PROCESS
2. ADIABATIC PROCESS
3. ISOBARIC PROCESS
4. ISOCHORIC PROCESS

For each case, the process is assumed to be quasi-

static

Which means that it occurs slowly enough that a

uniform pressure and temperature exist throughout all
regions of the system at all time.
ISOTHERMAL PROCESS (Very slow Process)

An isothermal process is one

where the temperature does not
change (same T).

Ex: When acid solution is added

very slowly to a base solution
without increasing the
temperature

On ideal gas, PV = nRT

becomes PV = constant.
PV diagram for an ideal gas
undergoing isothermal process
at two different temperature.
Temperature is keep constant, so the internal energy
does not change.

By the first law of thermodynamics:

 Vf 
w  nRTln  
 Vi 
So, in isothermal process:
 Pi 
w  nRTln  
 Pf 
The work done by the gas in isothermal process equal
the heat added to the gas
Example: 3
During an isothermal process, 5.0 J of heat is removed
from an ideal gas. What is the work done in the
process? Ans: -5.0 J
EXAMPLE 4
Two moles, of the monatomic gas argon expand
isothermally at 298 K, from an initial volume of Vi =
0.025 m3 to a final volume of Vf = 0.05 m3. Assuming
that argon is an ideal gas, find ;
a) the change in the internal energy of the gas. Ans: 0 J
b) b) The heat supplied to the gas. Ans: +3434.644 J
ADIABATIC PROCESS
An adiabatic process is one where there is no heat flow
into or out of the system.

ΔQ = 0.

Process on an ideal gas

in diagram for: - adiabatic
(AC) - isothermal (AB)
so, in adiabatic process;

3
u  nRT
2

The internal energy decreases if the gas expands;

hence the temperature decreases as well
(because Δ𝑈=32𝑛𝑅𝑇).
 Example 5
In an engine, an almost ideal gas is compressed
adiabatically to half its volume. In doing so, 1850 J of
work is done on the gas.
(a)How much heat flows into or out of the gas? Ans: 0J
(b)What is the change in internal energy of the gas?.
Ans: 1850 𝐽
 ISOBARIC PROCESS

An isobaric process

At constant pressure; the process is a straight

horizontal line on the PV diagram.
If the pressure is constant during the process
(ISOBARIC), the work done is the pressure multiplied
by the change in volume:

If Δ𝑉 𝑖𝑠 negative (since V is decrease);

W is then negative (- W).
That means, work is done on the gas

Q  mc
EXAMPLE 6

One gram of water is placed in the cylinder and the

pressure is maintained at 2 x 105 Pa. The temperature of
the water is raised by 31oC. In one case, the water is in
the liquid phase 0.5 x10-8 m3 and expands by the much
greater amount of 1 x 10-8 m3. Find:

a) The work done Ans: 0.001 J

b) the change in the internal energy .Ans: +130 J
ISOVOLUMETRIC PROCESS
An isovolumetric or
isochoric process is one in
which the volume does not
change.
In this process, the volume
does not change, so no work is
done, W = 0.
For processes where the
pressure varies, the work
done is the area
ENCLOSED in the P-V
curve

PV diagram for
adiabatic for different
processes, where the
system changes from A
to B.
1)When the pressure is constant, the work done is
equal to the shaded area is just PB (VB- VA)
When the temperature is constant, the work done is
equal to the shaded area shown in this graph.
EXAMPLE 7

Calculate the work done from A to C. Ans : 0.18 J

A brief summary of the process
THE SECOND LAW of THERMODYNAMICS

Definition: Example: Ice cream melts when left out on

warm day. It never become colder when left in hot
environment. Heat always flow spontaneously from hot
to cold and never from cold to hot.

THE SECOND LAW of THERMODYNAMICS “heat

flows spontaneously from a substance at a higher
temperature to a substance at a lower temperature
and does not flow spontaneously in the reverse
direction or it will not flow spontaneously from a
cold object to a hot object”.
Entropy and the Second Law of Thermodynamics

Definition of the change in entropy S when an amount

of heat Q is added:
T is in Kelvin

where
s  sH  sL s H 
QH sL 
QL
TH TL
Another statement of the second law of
thermodynamics: “The total entropy of an isolated
system never decreases”.
EXAMPLE: 8

An ice cube of mass 28 g is taken from a storage

compartment at 0oC and placed in a paper cup. After a
few minutes, exactly half of the mass of the ice cube
has melted, becoming water at 0oC. Find the change
in entropy of the ice/water. (L = 333 kJ/kg).
Ans:34.154 J/K
EXAMPLE: 8a

The figure shows 1200 J of heat flowing spontaneously through a copper

rod from a hot reservoir at 650 K to a cold reservoir at 350 K. Determine
the amount by which this irreversible process changes the entropy of the
universe, assuming that no other changes occur. Ans: 1.583 J/K

Hot reservoir, TH = 650 K

Copper
Rod
1200 J

Cold reservoir, TC = 350 K

 EXAMPLE: 8b

A sample of 50.0 kg of water at 20oC is mixed with

50.0 kg of water at 24oC. Calculate the change in
entropy(cwater = 4186 J/kgoC). Ans:9.6 J/K
The Carnot Cycle And Efficiency Of Engines

Mechanical energy can be obtained from thermal

energy only when heat can flow from a higher
temperature to a lower temperature.

Some of heat can then be transformed to mechanical

work.

We will discuss only engines that run in a repeating

cycle; (the change in internal energy over a cycle is
zero, as the system returns to its initial state).
Schematic
diagram of energy
transfer for a heat
engines.
The change in internal energy of the system is ΔU = 0
(it returns to the starting state).

A heat input, QH at a high temperature, TH is

transformed into work, W and partly exhausted as
heat, QL at a lower temperature, TL.

TH and TL are called the operating temperature of the

engine.

Conservation energy, QH = W + QL.

Now, QH , W, and QL as always positive.

A steam engine is one type of heat engine.
The internal combustion engine is a type of heat engine as
well.
HEAT ENGINE
The efficiency of the heat engine is the ratio of the work
done, W to the heat input at the high temperature:

W=work, QH = heat input

Using conservation of energy to eliminate W, we find:

QL = heat
discharged
Example 9

1) An automobile engine has an efficiency of 20% and

produces an average of 23, 000 J of mechanical
work per second during operation.
a) how much heat input is required. Ans :115 kJ
b) how much heat is discharged as waste heat from
this engine, per second? Ans: 92 kJ
EXAMPLE 10
A automobile engine has an efficiency of 22 % and
produces 2510 J of work. How much heat is rejected by
the engine? Ans: 8899.091 J
CARNOT ENGINE
The Carnot engine was created to examine the
efficiency of a heat engine.

It is idealized, as it has no friction. Each leg of its cycle

is reversible.

1. The Carnot cycle consists of:

2. Two are Isothermal expansion (T = 0)
3. Two are Adiabatic expansion (Q = 0)
The carnot cycle. Heat engines work in a cycle and the cycle for the
cycle engine begins at point „a‟ on this diagram.
1)The gas is first expanded isothermally, with the addition of heat QH,
along the path „ab‟ at temperature TH.
2)The gas expands adiabatically from „b to c‟ (no heat is exchanged,
but the temperature drops to T1).
3)The gas is then compresses at constant temperature, T1 (path cd)
and heat Q1 flows out.
4)Finally the gas is compressed adiabatically, path „da‟ back to its
original state.
CARNOT ENGINE

For an ideal reversible engine, the e

Real engines have some TH – Temperature

frictional losses; the best during addition of
achieve 60-80% of the Carnot heat in Kelvin
value of efficiency.
TL – Temperature
during exhaust of
heat in Kelvin
Example 11
What is the Carnot efficiency for a heat engine
operating between the temperature of 3000C and
150C is.
Ans : 49.7%
EXAMPLE 12
A steam engine operates between 450oC and 800oC.
What is the maximum possible efficiency of this steam
engine? Ans: 0.32619
EXAMPLE 13

An engine manufacturer makes the following claims: an

engine’s heat input per second is 9.0 kJ at 435 K. the
heat output per second is 4.0 kJ at 285 K. Do you believe
these claims? Calculate engine real efficiency and ideal
efficiency .Ans: 0.56, 0.34
EXAMPLE 14
Water near the surface of a tropical ocean has a
temperature of 25oC, whereas water 700 m beneath the
surface has a temperature of 7oC. It has been proposed
that the warm water be used as the hot reservoir and the
cool water as the cold reservoir of a heat engine. Find
the max possible efficiency for such an engine. Ans:
6.04%
Refrigerators, Air
Conditioners and heat pump

These appliances can be

thought of as heat engines
operating in reverse.

By doing work, heat is extracted

from the cold reservoir and
exhausted to the hot reservoir.

Schematic diagram of energy

transfer for heat pump,
refrigerator or air conditioner.
a)Typical refrigerator system
b)Schematic diagram.
Refrigerators and Air Conditioners

Refrigerator performance is measured by the

coefficient of performance (COP):
 HEAT PUMP

A heat pump can heat a house in the winter:

Heat pump equation:

A heat pump uses an

electric motor to „pump‟
heat from the cold outside
to the warm inside the
house. HEAT PUMP
𝑪𝑶𝑷=𝑸𝑯
EXAMPLE 15
A heat pump has a COP of 3 and is rated to do work at
1500 W. a) how much heat can it add to a room per
second? b) if the heat pump were turned around to act as
an air conditioner in the summer, what will you expect its
COP to be? Ans: 4500W, 2
EXAMPLE: 16
An ideal or Carnot heat pump is used to heat a house to a
temperature of TH = 294 K (21oC). How much work must
be done by the pump to deliver QH = 3350 J of heat into
the house when the outdoor temperature TL is a) 273 K
(0oC) b) 252 K (-21oC) Ans: 239.286 J, 478.571 J