INES-RUHENGERI ---- INSTITUTE OF APPLIED SCIENCES

FACULTY OF FUNDAMENTAL APPLIED SCIENCES

DEPARTMENT OF CIVIL ENGINEERING

MODULE: ENGINEERING PHYSICS

By Mr. MUHIRE Elisée

CONTACT: +250788421176 & [email protected]
UNIT IV: APPLIED THERMODYNAMICS

4.1 TEMPERATURE AND HEAT: temperature and thermal equilibrium, the zeroth law of
thermodynamics, thermometers and temperature scales, triple point of a substance, thermal
expansion, quantity of heat, specific heat, molar heat capacity, calorimetry and phase
changes, mechanisms of heat transfer (conduction, convection, and radiation).
4.2 THERMAL PROPERTIES OF MATTER: the states of matter, the state variables and the
equation of state of matter, molecular properties of matter (molecules and intermolecular
forces, moles and Avogadro’s number), kinetic theory of gases (microscopic view of gases,
pressure and molecular motion of gases, ideal gases, kinetic-molecular model of an ideal
gas (collisions and gas pressure, molecular kinetic energies, molecular speeds, the Maxwell-
Boltzmann distribution), heat capacities (heat capacities of gases, heat capacities of solids).
4.3 THE FIRST LAW OF THERMODYNAMICS: Thermodynamic systems, work done during
volume changes, internal energy of a physical system, the mechanical equivalent of heat,
kinds of thermodynamic processes (adiabatic process, isothermal process, isochoric
process, and isobaric process), the first law of thermodynamics.
4.4 THE SECOND LAW OF THERMODYNAMICS: Directions of thermodynamic processes,
heat engines (hot and cold reservoirs, efficiency of a heat engine), refrigerators, the second
law of thermodynamics, the Carnot cycle, and entropy).
Introduction
Thermodynamics: the study of energy transformations involving
heat, mechanical work, and other aspects of energy and how these
transformations relate to the properties of matter.

Thermodynamics forms an
indispensable part of the foundation of
physics, chemistry, and the life sciences,
and its applications turn up in such
places as car engines, refrigerators,
biochemical processes, and the
structure of stars.
Temperature and the Zeroth Law of Thermodynamics
Temperature and Thermal Equilibrium
Temperature is the degree of hotness or coldness of a body,
substance or space.
A body that feels hot usually has a higher temperature than a similar
body that feels cold.
Many properties of matter that we can measure depend on
temperature: The length of a metal rod, steam pressure in a boiler,
the ability of a wire to conduct an electric current, and the color of a
very hot glowing object—all these depend on temperature.
To use temperature as a measure of hotness or coldness, we need to
construct a temperature scale for temperature measurement. Figure below
(a) shows a familiar system (Thermometer) that is used to measure the
temperature. When the system becomes hotter, the colored liquid (usually
mercury or ethanol) expands and rises in the tube, and the value of L
increases. Another simple system is a quantity of gas in a constant-volume
container (Figure (b)). The pressure p, measured by the gauge, increases or
decreases as the gas becomes hotter or colder.

Using gas pressure …

Using expansion …
Heat definition
Heat - is the thermal energy that flows from
something of a higher temperature to
something of a lower temperature.
or
 Heat is the energy transferred between
objects because of a temperature
difference.
Note:
Objects are in thermal contact if heat can flow between
them. When the transfer of heat between objects in thermal
contact ceases, they are said to be in thermal equilibrium.

The zeroth law of thermodynamics: thermal equilibrium

Statement:
If object A is in thermal equilibrium with object B, and object
C is also in thermal equilibrium with object B, then objects A
and C will be in thermal equilibrium if brought into thermal
contact.
That is, the temperature is the only factor that determines whether
two objects in thermal contact are in thermal equilibrium or not.
We can discover an important property of
thermal equilibrium by considering three
systems, A, B, and C, that initially are not in
thermal equilibrium (Figure on the right
side).
A temperature difference causes heat energy to
flow to bring systems into thermal equilibrium
Another statement of the zeroth law of thermodynamics
Thermometers and Temperature Scales
 Thermometers are devices used to measure the temperature
according to well-defined scales of measurement.
 The three most common temperature scales are Fahrenheit,
Celsius, and Kelvin.
 Temperature scales are created by identifying two reproducible
temperatures: The freezing and boiling temperatures of water
at standard atmospheric pressure are commonly used.
On the Celsius scale, the freezing point of water is 0 °C and the
boiling point is 100 °C. The unit of temperature on this scale
is the degree Celsius (°C).
 The Fahrenheit scale (still the most frequently used for common
purposes in the United States) has the freezing point of water
at 32 °F and the boiling point of 212 °F. Its unit is the degree
Fahrenheit (°F).
 100 Celsius degrees span the same range as 180 Fahrenheit
degrees. Thus, a temperature difference of one degree on the
Celsius scale is 1.8 times as large as a difference of one degree on
the Fahrenheit scale
The Kelvin scale is the absolute temperature scale that is
commonly used in science. The SI temperature unit is the kelvin,
which is abbreviated K (not accompanied by a degree sign). Thus 0 K
is absolute zero. The freezing and boiling points of water are
273.15 K and 373.15 K, respectively. Therefore, temperature
differences are the same in units of kelvins and degree Celsius
Relationships among Kelvin (K), Celsius (C), and Fahrenheit (F)
temperature scales. Temperatures have been rounded off to the
nearest degree.
Conversion Between Temperature Scales
Converting Celsius to Fahrenheit:

Converting Fahrenheit to Celsius:

Converting Celsius to Kelvin:

Thermal Expansion
Most substances expand when heated; the change in length or
volume is typically proportional to the change in temperature.
The proportionality constant is called the coefficient of
linear(volume) expansion.
• Solids expand when heated
Increasing the temperature of a gas at
constant pressure causes the volume of the
gas to increase. (Also occurs in solids and
liquids)
In general, as the temperature of a
substance increases, the length/
area/volume also increases. This is known as
thermal expansion.
Linear Expansion
Suppose a rod of material has a length L0 at some initial temperature
T0. When the temperature changes by ΔT, the length changes by ΔL.
Experiments show that if ΔT is not too large (say, less than 100 °C or
so), ΔL is directly proportional to ΔT. If two rods made of the same
material have the same temperature change, but one is twice as
long as the other, then the change in its length is also twice as
great. Therefore ΔL must also be proportional to L0. Introducing a
proportionality constant α (which is a coefficient of linear expansion
and it is different for different materials), we may express these
relationships in an equation:
How the length of a rod changes with a change in temperature.
(Length changes are exaggerated for clarity.)

The constant α is called the coefficient of linear expansion.

Some typical coefficients of (thermal) Linear expansion:
Surface Expansion
The expansion of an area of a flat substance is derived from the
linear expansion in both directions:

Holes expand as well:

Volume Expansion

Increasing temperature usually causes increases in volume for

both solid and liquid materials. Just as with linear expansion,
experiments show that if the temperature change ΔT is not too
great (less than 100 °C or so), the increase in volume ΔV is
approximately proportional to both the temperature change and
the initial volume Vo:

The constant β characterizes the volume expansion properties of

a particular material; it is called the coefficient of volume
expansion.
Some typical coefficients of volume expansion:
Thermal Expansion of Water [The Unusual Behavior of Water]
Water, in the temperature range from 0°C to 4°C decreases in
volume with increasing temperature. In this range its coefficient of
volume expansion is negative. Above 4°C water expands when
heated. Hence water has its greatest density at 4°C. Water also
expands when it freezes, which is why ice humps up in the middle
of the compartments in an ice cube tray. By contrast, most
materials contract when they freeze.
Water also expands when it is
heated, except when it is close to
freezing; it actually expands when
cooling from 4 °C to 0 °C. This is why
ice floats and frozen bottles burst.
Heat Capacity and Specific Heat
• When heat energy flows into a substance, its temperature will increase.
• The heat capacity C of a particular sample of a substance is defined as the amount of
energy needed to raise the temperature of that sample by 1°C. From this definition, we
see that if heat Q produces a change ΔT in the temperature of a substance, then Q=C
ΔT.
• The specific heat capacity c is the heat energy (in J) needed to raise the temperature of
1 kg of the substance by 1 K. The specific heat capacity c of a substance is also the heat
capacity per unit mass.

Heat energy in J Temperature

change in K
Mass in kg
Specific heat
capacity in J/K/kg
The greater a material’s specific heat, the more energy must be added to a given mass of
the material to cause a particular temperature change.
Specific Heat
Specific heat is defined as the amount of thermal energy needed to
raise a unit mass of substance a unit of temperature. Its symbol is C.
For example, one way to express the specific heat of water is one
calorie per gram per degree Celsius: C = 1 cal / (g · °C), or 4.186 J / (g ·
°C). This means it would take 20 cal of thermal energy to raise 4 grams
of water at 5 °C.
Water has a very high specific heat, so it takes more energy to heat up
water than it would to heat up most other substances (of the same
mass) by the same amount. Oceans and lakes act like “heat sinks”
storing thermal energy absorbed in the summer and slowing releasing it
during the winter. Large bodies of water thereby help to make local
climates less extreme in temperature from season to season.
We can define a unit of quantity of heat based on temperature
changes of some specific material. The calorie (abbreviated cal) is
defined as the amount of heat required to raise the temperature of
1 gram of water from 14.5°C to 15.5°C. The kilocalorie (kcal), equal
to 1000 cal, is also used; a food-value calorie is actually a kilocalorie.
A corresponding unit of heat using Fahrenheit degrees and British
units is the British thermal unit, or Btu. One Btu is the quantity of
heat required to raise the temperature of 1 pound (weight) of water
1 from 63 °F to 64 °F
Specific Heat
Equation
Q = m C T
Q = thermal energy
m = mass
C = specific heat
T = change in temperature
Example: The specific heat of silicon is 703 J / (kg · ºC). How much
energy is needed to raise a 7 kg chunk of silicon 10 ºC ?
Answer:
Q = 7 kg ·703 J ·10 ºC = 49 210 J
kg · ºC
Note that the units do indeed work out to be energy units.
Example 2: Heat Capacity and Specific Heat
• Heat energy flows until equilibrium is reached

• Heat energy lost by frypan = Heat energy gained by water

• Total heat energy change = 0 (conservation of energy)

Example 3: A 32.0 g silver spoon cools from 60o C to 20oC. What
is the change in thermal energy? Take the specific heat of silver
to be 235 J/(kg.K).

m = 32.0g = 0.0320 kg
C = 235 J/(kg.K) –from table of values for silver
Tinitial =60oC
Tfinal =20oC Q = (m)( ΔT)(C)
= (0.0320 kg)(-40.0oC)(235J/kg . K)
= -301 J
The spoon loses 301 J of thermal energy as it cools.
CALORIMETRY AND PHASE CHANGES
Phase Changes

We use the term phase to describe a specific state of matter, such

as a solid, liquid, or gas. The compound exists in the solid phase as
ice, in the liquid phase as water, and in the gaseous phase as
steam. (These are also referred to as states of matter: the solid
state, the liquid state, and the gaseous state.) A transition from
one phase to another is called a phase change or phase transition.
For any given pressure, a phase change takes place at a definite
temperature, usually accompanied by absorption or emission of
heat and a change of volume and density.
Phases of matter
Gas - very weak
intermolecular forces,
rapid random motion
high temperature
low pressure
Liquid - intermolecular
forces bind closest neighbours

low temperature
Solid - strong high pressure
intermolecular forces
39
Phase Changes
 Phase changes (solid, liquid, gas) are accompanied by
release or absorption of heat energy
Heat for Phase Changes
 The amount of energy involved in a change of phase , per unit
mass, is known as the latent heat. The heat involved in a change
of phase depends not only on the latent heat but also on the
total mass of the substance. That is,

Q = heat energy absorbed/released [J]

m = mass of substance [kg]
L = latent heat [J/kg]
Melting ice
 The heat required per unit mass to melt ice-water is called the heat of
fusion (or sometimes latent heat of fusion), denoted by Lf. For water at
normal atmospheric pressure the latent heat of fusion is

 More generally, to melt a mass m of material that has a latent heat of

fusion Lf requires a quantity of heat Q given by:

We can go through this whole story again for boiling or

evaporation, a phase transition between liquid and gaseous
phases. The corresponding heat, per unit mass, is called the latent
heat of vaporization Lv . At normal atmospheric pressure the heat
of vaporization Lv for water is
 Graph of temperature
versus time for a specimen
of water initially in the
solid phase (ice) at -25 °C.
 Heat is added to the
specimen at a constant
rate.
 The temperature remains
constant during each
change of phase, provided
that the pressure remains
constant.
Heat Calculations: Simple model for heating a substance at a constant rate
T(t)
boiling
point
g
l /g
melting
point l
s s/l

Q(t)
mcsT mLf mclT mLv mcgT

44
 Phase changes at constant temperature
deposition
Q= ± m LS
LS latent heat of sublimation
sublimation
or heat of sublimation

freezing condensation

solid liquid gas

melting evaporation
Q= ± m Lf Q= ± m LV
At melting point: Lf latent heat of At boiling point: LV latent heat of
fusion or heat of fusion vaporization or heat of vaporization

Q > 0 energy absorbed by substance during phase change

Q < 0 energy released by substance during phase change
45
Specific heat Latent heats
Latent heat – phase change
Substance c (J.kg .K )
-1 -1
(formation or breakage of chemical
bonds requires or releases energy)
Aluminum 910
Copper 390 Water - large values of latent heats at
atmospheric pressure
Ice 2100 Lf = 3.34x105 J.kg-1 (273 K)
Water 4190 Lv = 2.26x106 J.kg-1(373 K)

Steam 2010
You can be badly scolded by
Air 1000 steam – more dangerous
Soils / sand ~500 than an equivalent amount of
boiling water WHY?
46
Latent heat and phase changes

As a liquid evaporates it extracts energy from its

surroundings and hence the surroundings are cooled.

When a gas condenses energy is released into the

surroundings.

Steam heating systems are used in buildings. A boiler

produces steam and energy is given out as the steam
condenses in radiators located in rooms of the building.

47
Conservation of Energy: Calorimetry—Solving Problems

A system is any object or set of objects that we wish to consider. Everything

else in the universe we will refer to as its “environment” or the
“surroundings.” There are several categories of systems. A closed system is
one for which no mass enters or leaves (but energy may be exchanged with
the environment). In an open system, mass may enter or leave (as may
energy). Many (idealized) systems we study in physics are closed systems.
But many systems, including plants and animals, are open systems since they
exchange materials (food, oxygen, waste products) with the environment. A
closed system is said to be isolated if no energy in any form passes across
its boundaries; otherwise it is not isolated.
When different parts of an isolated system are at different
temperatures, heat will flow (energy is transferred) from the
part at higher temperature to the part at lower temperature—
that is, within the system. If the system is truly isolated, no energy
is transferred into or out of it. So the conservation of energy again
plays an important role for us: the heat lost by one part of the
system is equal to the heat gained by the other part:
The exchange of energy is the basis for a technique known
as calorimetry, which is the quantitative measurement of
heat exchange. To make such measurements, a
calorimeter is used; a simple water calorimeter is shown in
Figure on right side. It is very important that the
calorimeter be well insulated so that almost no heat is
exchanged with the surroundings. One important use of
the calorimeter is in the determination of specific heats of
substances. In the technique known as the “method of
mixtures,” a sample of a substance is heated to a high
temperature, which is accurately measured, and then
quickly placed in the cool water of the calorimeter. The
heat lost by the sample will be gained by the water and
the calorimeter cup. By measuring the final temperature
of the mixture, the specific heat can be calculated.
EXAMPLE: Unknown specific heat determined by calorimetry.

An engineer wishes to determine the specific heat of a new metal alloy. A

0.150-kg sample of the alloy is heated to 540°C. It is then quickly placed in
0.400 kg of water at 10.0°C, which is contained in a 0.200-kg aluminum
calorimeter cup. (We do not need to know the mass of the insulating jacket
since we assume the air space between it and the cup insulates it well, so
that its temperature does not change significantly.) The final temperature of
the system is 30.5°C. Calculate the specific heat of the alloy if the specific
heats of water and aluminum are 4186 J/Kg ° C and 900 J/Kg ° C, respectively.
In making this calculation, we have ignored any heat transferred to the
thermometer and the stirrer (which is used to quicken the heat transfer
process and thus reduce heat loss to the outside). It can be taken into
account by adding additional terms to the right side of the above
equation and will result in a slight correction to the value of ca .
ENERGY TRANSFER MECHANISMS
[Mechanisms of Heat Transfer]
• How is heat energy transferred from one place to another?

conduction radiation

convection
Usually for a given situation one mechanism will dominate however in
some cases all three need to be considered simultaneously.
Conduction
• Heat transfer by direct molecular contact
Conduction
• Heat flow rate (H) increases with area and temperature drop
Q T
H A
t x
heat flows from
high T to low T
dT temperature
H  kA
dx gradient

thermal conductivity (W/m ˚C)

Heat flow is the rate of heat transfer by conduction. The larger the area the
greater the heat flow. The higher the thermal conductivity the greater the
heat flow. Heat flow is driven by a temperature gradient, so the larger the
temperature difference the greater the heat flow.
Heat transfer occurs only between regions that are at different
temperatures, and the direction of heat flow is always from
higher to lower temperature.
Thermal conduction
• Thermal conduction is the flow of heat by transfer of energy
between particles. It is due to the collision or diffusion of
particles along a gradient (higher kinetic energy to lower kinetic
energy).
• We usually think heating by conduction as a direct heat transfer
between materials.

Example: Heating food in a pot or pan

on the stove.
Thermal conductors
Thermal conductors are substances
that rapidly transfer energy as heat.

Metals are very good thermal conductors

Thermal insulators

Thermal insulators are substances

that slowly transfer heat.
R values for home Insulation
 The R-value indicates resistance to heat flow. The R-value of a
material is a measure of the resistance of that a 1 m x 1 m square
slab of material has , to heat flow per centimeter of the material’s
thickness.
Dead-Air Spaces as Insulation
Even though glass is a good insulator, windows
transfer thermal energy.
A single pane of glass has an R-value of 1.
A double-pane window traps air between the panes
to produce greater insulating properties.
Convection
Heat transfer by bulk motion of a fluid
Convection

Natural convection relies Forced convection drastically

on the buoyancy effect increases the fluid movement
alone to move the fluid. by using a fan or pump.

Calculations for convection are extremely complicated due to fluid dynamics

and remains one of the important unsolved problems in science.
Radiation
• Heat transfer by electromagnetic radiation
Transfer of heat in the form of waves. It does not
require matter to be present for transfer.
Heat from the sun that warms the Earth is an example
of radiant energy transfer.
Radiation
• Electromagnetic radiation?
Radiation
Radiation
Emissivity usually assumed to be e=1 in our problems –
sometimes called “black body emission”

Objects also absorb energy from surroundings at a rate

given by the same law
Radiation
The Sun radiates energy at the rate P = 3.9 x 1026 W, and its
radius is R = 7 x 108 m. Assuming the Sun is a perfect emitter
(e=1), what is its surface temperature?
Home Heating Systems

 Forced air (gas or oil furnace) convection–(uses fan in air

handler)
 Hot Water Radiators – radiation
 Fireplace – radiation & convection (with fan)
 Electric heater – radiation & convection (with fan – air
handler)
 Coal or wood stoves – radiant
EXERCISES
Phase Changes
Energy required to melt 1 kg of ice = 334 kJ

However, it depends on initial T, since water may boil!

Phase Changes

Energy is required to: (1) heat the ice cube to

0oC, (2) melt the ice cube
Q3= micecwater(T-0) = 0.02 × 4186 × T

Total energy = 123 + 6680+83.72 = 6886.72

J
Calculating the specific heat capacity
3. How much energy would be needed to heat 450 grams of copper metal
from a temperature of 25.0 °C to a temperature of 75.0 °C? (The specific
heat of copper at 25.0 °C is 0.385 J/g °C.)

Solution:
The change in temperature (ΔT) is: 75° C - 25 °C = 50 °C
Given mass, two temperatures, and a specific heat capacity,
you have enough values to plug into the specific heat
equation Q = m x C x ΔT and plugging in your values you get
Q= (450 g) x (0.385 J/g °C) x (50.0 °C)= 8700 J
4. A 5-kg cube of warm iron (60°C) is put in thermal contact with a 10-kg
cube of cold iron (15°C). Which statement is valid:

(a) Heat flows spontaneously from the warm cube to the cold cube until
both cubes have the same heat content.
(b) Heat flows spontaneously from the warm cube to the cold cube until
both cubes have the same temperature.
(c) Heat can flow spontaneously from the warm cube to the cold cube, but
can also flow spontaneously from the cold cube to the warm cube.
(d) Heat can never flow from a cold object or area to a hot object or area.
(e) Heat flows from the larger cube to the smaller one because the larger
one has more internal energy.
5. How heat transferred depends on specific heat.
(a) How much heat input is needed to raise the temperature of an
empty 20-kg iron vat made of iron from 10 °C to 90 °C? (b) What if
the iron vat is filled with 20 kg of water?
6. The cup cools the tea. If 200 cm3 of tea at 95°C is poured
into a 150-g glass cup initially at 25°C (Figure below), what will
be the common final temperature T of the tea and cup when
equilibrium is reached, assuming no heat flows to the
surroundings? Density of water is d=1.0 ×103 kg/m3, Specific
heats of cup and that of water are 840 and 4186 J/Kg °C, respectively.
NOTE:
The cup increases in temperature by 86°C - 25°C = 61 C°. Its
much greater change in temperature (compared with that of
the tea water) is due to its much smaller specific heat
compared to that of water.
7. Taking your temperature. Normal body temperature is
98.6°F. What is this on the Celsius scale?
8. Bridge Expansion. The steel bed of a suspension bridge is 200
m long at 20 °C. If the extremes of temperature to which it
might be exposed are -30 °C to +40 °C/ to how much will it
contract and expand? Coefficient of expansion is α=12×10-6/ °C
9. Ring on a rod.
An iron ring is to fit snugly (closely) on a cylindrical iron rod. At 20°C,
the diameter of the rod is 6.445 cm and the inside diameter of the ring
is 6.420 cm. To slip over the rod, the ring must be slightly larger than
the rod diameter by about 0.008 cm. To what temperature must the
ring be brought if its hole is to be large enough so it will slip over the
rod? Coefficient of expansion is α=12×10-6/ °C
10. Gas tank in the Sun. The 70-liter (L) steel gas tank of a car is filled to the
top with gasoline at 20°C. The car sits in the Sun and the tank reaches a
temperature of 40°C. How much gasoline do you expect to overflow from
the tank? The coefficient of volume expansion of gasoline is 950×10-6/°C.
Coefficient of linear expansion of steel is α=12×10-6/ °C.
11. A major source of heat loss from a house is through the
windows. Calculate the rate of heat flow through a glass window
2.0 m × 1.5 m in area and 3.2 mm thick, if the temperatures at
the inner and outer surfaces are 15.0°C and 14.0°C, respectively
(Figure below). The conductivity K=0.84J/s m °C.
12. Cooling by radiation. An athlete is sitting unclothed in a
locker room whose dark walls are at a temperature of 15°C.
Estimate his rate of heat loss by radiation, assuming a skin
temperature of 34 °C and Ɛ=0.70. Take the surface area of the
body not in contact with the chair to be 1.5 m2. Stefan Boltzmann
constant is 5.67 ×10-8 W/m2.K4
13. You place a small piece of ice in your mouth. Eventually, the
water all converts from ice at T1=32.0 °F to body temperature
T2=98.60°F, Express these temperatures in both Celsius degrees
and kelvins, and find ΔT=T2-T1 in both cases.
14. A surveyor uses a steel measuring tape that is exactly
50.000 m long at a temperature of 20°C. The markings on the
tape are calibrated for this temperature. What is the length of
the tape when the temperature is 35°C? The value of α for steel
is 1.2×10-5/K.
15. A temperature change with no phase change
A camper pours 0.300 kg of coffee, initially in a pot at 70 °C into a 0.120-kg
aluminum cup initially at 20 °C. What is the equilibrium temperature? Assume
that coffee has the same specific heat as water (cwater=4186J/Kg °C) and that
no heat is exchanged with the surroundings. The specific heat of aluminum is
cal=900J/Kg °C.
16. Will all the ice melt? A 0.50-kg chunk of ice at – 10°C is placed
in 3.0 kg of “iced” tea at 20°C. At what temperature and in what
phase will the final mixture be? The tea can be considered as
water. Ignore any heat flow to the surrounding. Lf=333KJ/Kg. The
specific heat of ice is 2100 J/Kg °C.
APPROACH: Before we can write down an equation applying conservation of energy,
we must first check to see if the final state will be all ice, a mixture of ice and water at
0°C, or all water. To bring the 3.0 kg of water at 20°C down to 0°C would require an
energy release
17. Determining a latent heat. The specific heat of liquid mercury
is 140 J/kg °C. When 1.0 kg of solid mercury at its melting point of
– 39°C is placed in a 0.50-kg aluminum calorimeter filled with 1.2
kg of water at 20.0°C, the mercury melts and the final
temperature of the combination is found to be 16.5°C. What is the
latent heat of fusion of mercury in J/kg? The specific heat of water
is 4186 J/kg °C and that of aluminum is 900 J/kg °C.
18.
21.
21.
GROUP WORK

What mass of steam initially at 130°C is needed to warm

200 g of water in a 100-g glass container from 20.0°C to
50.0°C? The specific heats of water and steam are 4186
and 2010 J/Kg °C , respectively. The latent heat of
vaporization of water is 2.26 ×106 J/kg; and the specific
heat of glass is 837 J/Kg °C.
4.2 THERMAL PROPERTIES OF MATTER
MACROSCOPIC DESCRIPTION OF AN IDEAL GAS
Suppose that an ideal gas (a low-density gas) of mass m is confined to a cylindrical
container whose volume V can be varied by means of a movable piston. Let the
mass (or the number of moles) of the gas remains constant. For such a system,
experiments provide the following information: First, when the gas is kept at a
constant temperature, its pressure is inversely proportional to its volume
(Boyle’s law). Second, when the pressure of the gas is kept constant, its volume
or pressure is directly proportional to its temperature (the law of Charles and
Gay–Lussac). These observations are summarized by the equation of state for an
ideal gas.
 In an ideal gas, all the internal energy is in the form of kinetic
energy and any change in internal energy is accompanied by a
change in temperature.
 An ideal gas can be characterized by three state variables:
absolute pressure (P), volume (V), and absolute temperature (T).

The Gas Laws and Absolute Temperature

The relationship between the volume, pressure, temperature,

and mass of a gas is called an equation of state of an ideal
gas. We will deal here with gases that are not too dense.
Law
The Boyle’s Law describes the relationship stating that
when the gas is kept at a constant temperature, its
pressure is inversely proportional to its to its volume.
P1 V1 = P2V2
With the same amount of gas , the volume
increases while the pressure decreases.

V
Law
Charles’ Law describes the relationship stating that when
the pressure of the gas is kept constant, its volume is
directly proportional to its temperature.
V1 V2
T1
= T
2
V

T
With the same amount of gas, the volume increases as the
temperature increases. If the temperature decreases then the
volume also decreases.
Gay-Lussac’s
Law The pressure and absolute temperature
(K) of a gas are directly proportional at
constant mass & volume.

P1 P2
P
=
T1 T2
T
For a gas at constant mass and volume, the pressure and
temperature are directly related.
The laws of Boyle, Charles, and Gay-Lussac are not really
laws in the sense that we use this term today (precise,
deep, wide-ranging validity). They are really only
approximations that are accurate for real gases only as long
as the pressure and density of the gas are not too high, and
the gas is not too close to liquefaction (condensation).
Combined ideal Gas
Law
• It is a law that combines the previous laws into one.
PV = nRT
P1V1 P2V2  UNIVERSAL GAS CONSTANT

=
T1 T2
P 1V 1T 2 = P 2V 2T 1
The equation PV=nRT is called the ideal gas law, or the equation of state for an ideal gas. We use the
term “ideal” because real gases do not follow this equation, precisely, particularly at high pressure
(and density) or when the gas is near the liquefaction point (=boiling point). Always remember,
when using the ideal gas law, that temperatures must be given in kelvins (K) and that the pressure P
must always be absolute pressure, not gauge pressure.
Ideal Gas Law in Terms of
Molecules: Avogadro’s Principle
• For any ideal gas at constant temperature &
pressure, equal volumes of gases contain equal
numbers of molecules.
V1 V2
n1
= n
2

n
What does it mean?
For a gas at constant temperature and pressure, the
volume is directly proportional to the number of
moles of gas.
pressure
volume

Since the gas constant is universal, the number of

molecules in one mole is the same for all gases. That
number is called Avogadro’s number: NA = 6.02 × 1023
The number of molecules in a gas is the number of
moles times Avogadro’s number: N = nNA
Therefore we can write:

The ideal gas law

where k is called Boltzmann’s constant.

Dalton’s Law of Partial
Pressures
The total pressure of a mixture of gases equals the
sum of the partial pressures of the individual gases.
Ptotal = P1 + P2 + ...
Problem Solving strategies with the Ideal Gas Law
Useful facts and definitions:
Standard temperature and pressure (STP)
T = 273 K (0°C); P = 1.00 atm = 1.013 × 10 5 N/m2 = 101.3
kPa
Volume of 1 mole of an ideal gas is 22.4 L
If the amount of gas does not change:

Always measure T in kelvins.

P must be the absolute pressure not gauge pressure where
P=Pgauge + Po.
Obviously, the higher the temperature, the higher the pressure exerted by the
trapped gas. Of course, if the pressure increases high enough, the can will
explode. Because of this possibility, you should never dispose of spray cans in a
fire.
Exercise 3: Determine the volume of 1.00 mol of any gas, assuming it
behaves like an ideal gas, at STP. This means that:

SOLUTION: We solve for V in PV=nRT

Exercise 4: Helium balloon. A helium party balloon, assumed to be a perfect

sphere, has a radius of 18.0 cm. At room temperature (20°C), its internal
pressure is 1.05 atm. Find the number of moles of helium in the balloon and
the mass of helium needed to inflate the balloon to these values.
Exercise 5: An automobile tire is filled to a constant gauge pressure of 200
kPa at 10°C. After a drive of 100 km, the temperature within the tire rises to
40°C. What is the pressure within the tire now?
Exercise 6:

Exercise 7:
Differences Between Ideal and Real Gases
Ideal Gas Real Gas

Obey PV=nRT Always Only at very low

P and high T
Molecular volume Zero Small but
nonzero
Molecular attractions Zero Small

Molecular repulsions Zero Small

The Kinetic Theory of Gases
The molecular basis of thermal physics (microscopic view of gases,
pressure and molecular motion of gases, the velocity distribution of
gases, the Maxwell-Boltzmann distribution).

ASSIGNMENT

Derive the equation for the “Maxwell–Boltzmann distribution

function” and the equation for average speed by using the
distribution of molecular speeds aspects
The Molecular Basis Of Thermal Physics
A Microscopic View of Gases
Assumptions of the molecular model of an ideal gas
• The number of molecules is large, and the average separation between molecules is great compared
with their dimensions. This means that the volume of the molecules is negligible when compared with
the volume of the container.
• The molecules obey Newton’s laws of motion, but as a whole they move randomly. By “randomly”
we mean that any molecule can move in any direction with equal probability. We also assume that the
distribution of speeds does not change in time, despite the collisions between molecules. That is, at any
given moment, a certain percentage of molecules move at high speeds, a certain percentage move at
low speeds, and a certain percentage move at speeds intermediate between high and low.
• The molecules undergo elastic collisions with each other and with the walls of the container. Thus,
in the collisions, both kinetic energy and momentum are constant.
• The forces between molecules are negligible except during a collision. The forces between molecules
are short-range, so the molecules interact with each other only during collisions.
• The gas under consideration is a pure substance. That is, all of its molecules are identical.
A Microscopic View of Gases
Figure on the left side shows a cubical box with sides
of length d containing an ideal gas. The molecule
shown moves with velocity v.
Consider the elastic collision between one molecule of
mass m moving with a velocity v toward the right-hand
face of the box and the walls of the box.

The change in momentum of the molecule is

Applying the impulse–momentum theorem to the molecule gives

Over a time interval that is long compared with Δt, the average force exerted
on the molecule for each collision is

According to Newton’s third law, the average force exerted by the molecule
on the wall is equal in magnitude and opposite in direction to the force in
Equation above:

Each molecule of the gas exerts a force F 1 on the wall. We find the total force
F exerted by all the molecules on the wall by adding the forces exerted by the
individual molecules:
Pressure and Molecular Motion of gases

Having a box containing dilute gas of volume V at a temperature

T.
Average velocity in any direction is zero – there is no net
movement of the gas:

The brackets are used to indicate average value.

Pressure and Molecular Motion
Internal energy U comes mostly from the kinetic energies of the
molecules:

The average squares of velocities in all three directions are the

same:
Pressure and Molecular Motion

Now, relate to the pressure of the gas:

Pressure comes from the collisions of molecules with the walls of
the container.
If we look at a wall in the y-z plane, only the x-component of the
molecules’ momentum transfers momentum to it:
Pressure and Molecular Motion
Take imaginary cylindrical volume that abuts the wall.
Left: the volume
Right: the x-components are the only ones that matter here
Pressure and Molecular Motion
If the number density of molecules (same in the cylinder as in the
rest of the gas) is N/V, then the number of collisions in time dt is:

And the momentum transfer is:

Pressure and Molecular Motion

Finally, using the rms value of the velocity”

This is important!
Microscopic properties have been used to find a relation between
macroscopic thermodynamic variables.
The pressure is
proportional to the
number of
molecules per unit
volume and to the
average
translational kinetic
energy of the
molecules
Pressure and Molecular Motion
The force is the momentum transfer per unit time:

The pressure is the force per unit area:

The Meaning of Temperature
Since internal energy is related to pressure and volume, it is also
related to temperature:

The average kinetic energy of the molecules:

Temperature is proportional to average kinetic energy

That is, temperature is a direct measure of average molecular kinetic

energy.
The Meaning of Temperature
Average speed is not zero, though; we take the square of the
speeds (which is positive), average it, and then take the square
root. This is the rms (root mean square) value, and is never
negative:
The Meaning of Temperature
We can also understand the van der Waals equation better now.
It includes the effects of intermolecular forces, which act over
distances larger than the size of the molecule, are repulsive at
short range, and slightly attractive at longer distances.
Probability Distributions
Not all molecules have the average velocity, of course; for a more
complete description we need a velocity distribution function,
which tells us how many molecules have any particular velocity.
The position distribution function does the same thing for the
molecules’ location in space.
Probability Distributions
There are enough molecules in a macroscopic gas sample that the
distributions can be considered to be continuous. We define the probability
that a value lies within an interval Δx around a value x:

The probabilities are normalized so that

the total value is one – x must be
something.
The Velocity Distribution of Gases
First, define a velocity probability function:

This is the probability that the velocity lies between and

:

Assumption:
• Any way in which a gas’s total energy and total
momentum can be shared among the molecules is
equally likely.
The Velocity Distribution of Gases
Taking into account the individual and average kinetic energies, and how
many ways different states of the gas can be created, the distribution function
is found to be:

Now, we can use this function to calculate the average of the square of the
velocity:

With some manipulation, this can be turned into an integral that can be
looked up; finally:
The Maxwell-Boltzmann Distribution
The velocity distribution for an ideal gas can be written:

Here, E is the total energy of a molecule, and Z is a factor that ensures

proper normalization.
A diatomic molecule can do more than just move – it can rotate or vibrate,
and both contribute to its total kinetic energy. Including just the rotation:
The Maxwell-Boltzmann Distribution
Therefore, while the average kinetic energy of translation is

The addition of rotations about two axes adds two more factors
of ½ kT:

Finally, the addition of vibration contributes two more factors of ½ kT,

one for the motion of the atoms and one for the energy in the “spring”:
The Maxwell-Boltzmann Distribution

So, each possible independent motion is seen to add ½ kT to the

energy of the molecule; these are called degrees of freedom.
Contributing to the 7/2 kT above, we have:
• velocity in x, y, and z
• rotation about two different axes
• vibration, which includes two contributions
The Maxwell-Boltzmann Distribution
Therefore, we have the equipartition theorem, which states that
each degree of freedom contributes ½ kT to the average energy of
a molecule. For s degrees of freedom:

We can now relate this to the internal energy:

The constant multiplying the temperature is the constant-volume heat

capacity of the gas:
The Maxwell-Boltzmann Distribution
For molecular hydrogen:
QUIZ
1. A surveyor uses a steel measuring tape that is exactly 50 m
long at a temperature of 20°C. The markings on the tape are
calibrated for this temperature. What is the length of the
tape when the temperature is 35°C? The value of α for steel
is 1.2×10-5/K.
2. State the three mechanisms of heat transfer.

3. How much heat input is needed to raise the temperature of

an empty 20-kg iron vat from 10 °C to 90 °C? The specific
heat of iron is 450 J/kg °C
4.3 HEAT FLOW AND THE 1ST LAW OF
THERMODYNAMICS
 This section focuses on the concept of internal
energy, the processes by which energy is
transferred, the first law of thermodynamics, and
some of the important applications of the first law.

 The first law of thermodynamics is the law of

conservation of energy. It describes systems in
which the only energy change is that of internal
energy, which is due to transfers of energy by heat or
work.
HEAT AND INTERNAL ENERGY
Internal energy is all the energy of a system that is associated with its
microscopic components—atoms and molecules—when viewed from a
reference frame at rest with respect to the object.
 Internal energy includes kinetic energy of translation, rotation, and vibration of molecules,
potential energy within molecules, and potential energy between molecules.
 The internal energy of a monatomic ideal gas is associated with the translational motion of
its atoms. This is the only type of energy available for the microscopic components of this
system. In this special case, the internal energy is simply the total kinetic energy of the
atoms of the gas; the higher the temperature of the gas, the greater the average kinetic
energy of the atoms and the greater the internal energy of the gas.
WORK AND HEAT IN THERMODYNAMIC PROCESSES

Heat
Definition
Heat is defined as the transfer of energy across the boundary of a
system due to a temperature difference between the system and its
surroundings. When you heat a substance, you are transferring energy
into it by placing it in contact with surroundings that have a higher
temperature. This is the case, for example, when you place a pan of
cold water on a stove burner—the burner is at a higher temperature
than the water, and so the water gains energy.
The work
Definition

The work done on a system is a measure of the amount of energy

transferred to the system from its surroundings, whereas the
mechanical energy of the system (kinetic or potential, or both) is a
consequence of the motion and relative positions of the members of
the system. Thus, when a person does work on a system, energy is
transferred from the person to the system.
The 1st Law of Thermodynamics
Statement: The first law of thermodynamics states that when a system
undergoes a change from one state to another, the change in its internal
energy is
where Q is the heat energy transferred into the system and W is the work done
by the system. Although Q and W both depend on the path taken from the
initial state to the final state, the quantity ΔU is path-independent. This central
equation is a statement of conservation of energy that includes changes in
internal energy.
The quantity ΔU is determined completely by the initial and final
states of the system, and it is called the change in the internal
energy of the system. Although Q and W both depend on the path,
the quantity ΔU = Q - W is independent of the path.
NOTE:
The internal energy of a system would be increased if
work was done on the system, or if heat 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 on something in the surroundings.

We can now think about energy transfer into and out of
these systems; through
– heat transfer Q and
– work done W
The First Law of Thermodynamics
The coexistence of the work done by the system, which requires that there be
a macroscopic displacement of the point of application of a force (or pressure),
and the heat, which occurs through random collisions between the molecules
of the system result in a change in the internal energy of the system and
therefore usually result in measurable changes in the macroscopic variables of
the system, such as the pressure, temperature, and volume of a gas.
 The first law of thermodynamics is a statement of the conservation of energy.
 If a system’s volume is constant, and heat is added, its internal energy
increases.
The First Law of Thermodynamics

If a system does work on the external world, and no heat

is added, its internal energy decreases.
The First Law of Thermodynamics
Combining the above statememts gives the first law of
thermodynamics. The change in a system’s internal
energy is related to the heat Q and the work W as
follows:
It is vital to keep track of the signs of Q and W.
The Figure shows a gas that expands quasi-statically
(slowly) from state i to state f. The work done by the gas
equals the area under the PV curve.

The total work done by the gas as its volume changes from V i to Vf is
given by the integral:
The average squares of velocities in all three directions are the same:
Application of the 1st law: Thermodynamic PROCESSES

Process Terminology
Adiabatic Process
• An adiabatic process transfers no heat energy
• therefore Q = 0
• ΔU = Q – W Then ΔU = – W
• When a system expands adiabatically, W is positive (the system does
work) so the internal energy ΔU is negative.
• When a system compresses adiabatically, W is negative (work is done
on the system) so the internal energy ΔU is positive.

Another way to ensure that a process is

effectively adiabatic is to have the volume change
occurs very quickly.
In this case, heat has no time to flow in or out of
the system.
Isothermal Process
• An isothermal process is a constant
temperature process. Any heat flow into or
out of the system must be slow enough to
maintain thermal equilibrium
• For ideal gases, if ΔT is zero, ΔU = 0
• Therefore, Q = W
• Any energy entering the system (Q) must
leave as work (W)
Isochoric
Process
• An isochoric process is a constant volume
process. When the volume of a system
doesn’t change, it will do no work on its
surroundings.
• W=0
• ΔU = Q
• Heating gas in a closed container is an
isochoric process
Isobaric
Process
• An isobaric process is a constant pressure
process. ΔU, W, and Q are generally non-
zero, but calculating the work done by an
ideal gas is straightforward
W = P·ΔV
• Water boiling in a saucepan is an example
of an isobaric process
Summary on Thermal Processes

Here is a summary of the different types of thermal

processes:
Molar Specific Heats for an Ideal Gas:
Constant Pressure and Constant Volume
Specific heats for ideal gases must be quoted either at
constant pressure or at constant volume.

1. For a constant-volume process, we have:

Molar Specific Heats for an Ideal Gas:
Constant Pressure, Constant Volume
2. At constant pressure, we have:
Molar Specific Heats for an Ideal Gas:
Constant Pressure, Constant Volume
Both CV and CP can be calculated for a monatomic ideal gas
using the first law of thermodynamics.

and

and
Molar Specific Heats for an Ideal Gas:
Constant Pressure, Constant Volume
The P-V curve for an adiabatic cycle is given by
Definition: an adiabatic process is one in which no energy is exchanged
by heat between a system and its surroundings.
For example, if a gas is compressed (or expanded) very rapidly, very little
energy is transferred out of (or into) the system by heat, and so the process is
nearly adiabatic.
All three variables in the
where ideal gas law—P, V, and T
—change during an
adiabatic
process.
Examples of calculation
Notice that we use the initial temperature and volume to
determine the value of the constant pressure because we
do not know the final temperature. The work done by
the gas is negative because the gas is being compressed.
4.4 THE SECOND LAW OF THERMODYNAMICS, HEAT
ENGINES, AND THE ENTROPY
The Second Law The second law comes in many equivalent forms
 It is impossible to build a cyclic machine that converts heat into
work with 100% efficiency  Kelvin’s statement of the second
law.
 It is impossible to construct a cyclic machine that completely
(with 100% efficiency) converts heat, which is energy of
random molecular motion, to mechanical work, which is
ordered motion.
 The unavailable work is due to the role of Entropy in the
process.
Heat q 100% Kelvin’s
Heat reservoir Cyclic engine Work (w)  statement of the
second law
Not possible
Another statement of the second law → the Clausius statement

 Heat does not ‘flow’ from a colder body to a hotter body, without
an concomitant change outside of the two bodies Clausius’s
statement of the second law.
 This automatically implies that the spontaneous direction of the
‘flow of heat’ is from a hotter body to a colder body.
 The Kelvin’s and Clausius’s statements of the second law are
equivalent. I.e. if we violate Kelvin’s statement, then we will
automatically violate the Clausius’s statement of the second law
(and vice-versa).
A combined (Kelvin + Clausius) statement of the 2nd Law

 The entropy of a closed system will increase during any spontaneous

change/process.
If we consider the Universe to be a closed system (without proof!!), then
 The entropy of the universe will increase during any spontaneous change (process).

 Heat cannot spontaneously flow from a cold (low temperature) body to

a hot (high temperature) body.
 To make heat flow from a cold body to a hot body, there must be
accompanying change elsewhere (work has to be done to achieve this).
The Second Law of Thermodynamics

We observe that heat always flows spontaneously from a warmer

object to a cooler one, although the opposite would not violate
the conservation of energy. This direction of heat flow is one of
the ways of expressing the second law of thermodynamics:
When objects of different temperatures are brought into thermal
contact, the spontaneous flow of heat that results is always from
the high temperature object to the low temperature object.
Spontaneous heat flow never proceeds in the reverse direction.
Heat Engines
A heat engine is a device that converts heat into work.
A heat engine carries some working substance
through a cyclic process during which:
(1) the working substance absorbs energy by heat
from a high-temperature energy reservoir,
(2) work is done by the engine, and
(3) energy is expelled by heat to a lower-
temperature reservoir.
Example: the steam engine.
Characteristics of a Heat Engines
All heat engines have:
• a high-temperature reservoir
• a low-temperature reservoir
• a cyclical engine
These are illustrated schematically here.
The engine absorbs a quantity of energy Qh from the hot reservoir, it does
work W, and then gives up a quantity of energy Qc to the cold reservoir.
Because the working substance goes through a cycle, its initial and final
internal energies are equal, and so ΔU=0. Hence, from the first law of
thermodynamics, and with no change in internal energy, the net work W
done by a heat engine is equal to the net energy Q net flowing through it.
Steam Engine and Internal Combustion Engine
•Steam engines make use of steam heated by combustion of coal, oil or gas,
or by nuclear energy. The steam engine uses water as the working substance.
The water in a boiler absorbs energy from burning fuel and evaporates to
steam, which then does a work by expanding against a piston, forcing it to
move. After the steam cools and condenses, the liquid water produced
returns to the boiler and the cycle repeats.
Steam Engine and Internal Combustion Engine

For instance, in a typical process by which a power plant

produces electricity, coal or some other fuel is burned, and
the high-temperature gases produced are used to convert
liquid water to steam. This steam is directed at the blades
of a turbine, setting it into rotation. The mechanical energy
associated with this rotation is used to drive an electric
generator. Another heat engine which is the internal
combustion engine in an automobile—uses energy from a
burning fuel to perform work that results in the motion of
the automobile.
Heat Engines and the Carnot Cycle
The thermal efficiency “e” of a heat engine is defined as the
ratio of the net work done by the engine during one cycle to the
energy absorbed at the higher temperature during the cycle:

OR
The efficiency is the fraction of the heat supplied to the engine
that appears as work to the heat absorbed.
Real engines have efficiency
between 0 and 1

In order for the engine to run, there must be a temperature

difference; otherwise heat will not be transferred.
A heat engine has 100% efficiency (e = 1) only if Qc = 0—that is, if no energy is
expelled to the cold reservoir. In other words, a heat engine with perfect efficiency
would have to expel all of the absorbed energy as mechanical work. On the basis of
the fact that efficiencies of real engines are well below 100%, the Kelvin–Planck
form of the second law of thermodynamics states the following:

Kelvin–Planck statement of the second law of thermodynamics

It is impossible to construct a heat engine that, operating in a cycle, produces no
effect other than the absorption of energy from a reservoir and the performance of
an equal amount of work.

This statement of the second law means that, during the operation of a heat engine, W can
never be equal to Qh , or, alternatively, that some energy Qc must be rejected to the
environment.
Figure on the left side shows the schematic diagram of
a heat engine that absorbs energy Qh from a hot
reservoir and does an equivalent amount of work. It is
impossible to construct such a perfect engine.
The Carnot Engine: A heat engine operating in an ideal, reversible
cycleThe maximum-efficiency of heat engine is described in Carnot’s theorem:

If an engine operating between two constant-temperature reservoirs is

to have maximum efficiency, it must be an engine in which all processes
are reversible. In addition, all reversible engines operating between the
same two temperatures, Tc and Th, have the same efficiency. This is an
idealization; no real engine can be perfectly reversible.
If the efficiency depends only on the two temperatures, the ratio of
the temperatures must be the same as the ratio of the transferred
heats. Therefore, the maximum efficiency of a heat engine can be
written:
The Carnot Engine: A heat engine operating in an ideal, reversible cycle
The maximum work a heat engine can do is then:

If the two reservoirs are at the same

temperature, the efficiency is zero; the smaller
the ratio of the cold temperature to the hot
temperature, the closer the efficiency will be 1.
Figure shows the PV diagram for the Carnot cycle. The net work
done, W, equals the net energy received in one cycle,
Note that for the cycle.
1. Process A → B (Fig. a) is an isothermal expansion at
temperature Th. The gas is placed in thermal contact with an
energy reservoir at temperature Th. During the expansion, the
gas absorbs energy |Qh| from the reservoir through the base of
the cylinder and does work WAB in raising the piston.
2. In process B → C (Fig. b), the base of the cylinder is
replaced by a thermally nonconducting wall and the gas
expands adiabatically; that is, no energy enters or leaves the
system by heat. During the expansion, the temperature of the
gas decreases from Th to Tc and the gas does work WBC in
raising the piston.
3. In process C → D (Fig. c), the gas is placed in thermal
contact with an energy reservoir at temperature Tc and is
compressed isothermally
at temperature Tc. During this time, the gas expels energy |Qc|
to the reservoir and the work done by the piston on the gas is
WCD.
4. In the final process D → A (Fig. d), the base of the
cylinder is replaced by a nonconducting wall and the gas is
compressed adiabatically. The temperature of the gas
increases to Th, and the work done by the piston on the gas is
WDA.
FIGURE 4 Four-stroke-cycle- internal combustion engine:
(a) The gasoline–air mixture flows into the cylinder as the piston moves down;
(b) The piston moves upward and compresses the gas;
(c) The brief instant when firing of the spark plug ignites the highly compressed gasoline–air mixture, raising it to a
high temperature;
(d) The gases, now at high temperature and pressure, expand against the piston in this, the power stroke;
(e) The burned gases are pushed out to the exhaust pipe; when the piston reaches the top, the exhaust valve closes
and the intake valve opens, and the whole cycle repeats. (a), (b), (d), and (e) are the four strokes of the cycle.
Example 2: A steam engine has a boiler that operates at 500 K. The energy
from the burning fuel changes water to steam, and this steam then drives a
piston. The cold reservoir’s temperature is that of the outside air,
approximately 300 K. What is the maximum thermal efficiency of this
steam engine?
Solution Using Equation for the maximum thermal efficiency for any
engine operating between these temperatures is

Example 3: The highest theoretical efficiency of a certain engine is 30%. If

this engine uses the atmosphere, which has a temperature of 300 K, as its
cold reservoir, what is the temperature of its hot reservoir?
Solution: We use the Carnot efficiency to find Th :
Refrigerators, Air Conditioners, and Heat Pumps
While heat will flow spontaneously only from a higher
temperature to a lower one, it can be made to flow the other
way if work is done on the system. Refrigerators, air
conditioners, and heat pumps all use work to transfer
heat from a cold object to a hot object; and they are
heat engines running in reverse.
In a refrigerator or heat pump, the engine absorbs energy Qc from a cold
reservoir and expels energy Qh to a hot reservoir. This can be accomplished
only if work is done on the engine.
Refrigerators, Air Conditioners, and Heat
Pumps
If we compare the heat
engine and the refrigerator,
we see that the refrigerator is
basically a heat engine
running backwards – it uses
work to extract heat from the
cold reservoir.

A reservoir (the inside of the refrigerator) exhausts to the kitchen.

Note that
More heat is exhausted to the kitchen than is removed from the
refrigerator.
The operating principle of refrigerators, air conditioners, and heat pumps is just
the reverse of a heat engine. Each operates to transfer heat out of a cool
environment into a warm environment. By doing work W, heat is taken from a low-
temperature region, (such as inside a refrigerator), and a greater amount of heat
is exhausted at a high temperature, (the room). You can often feel this heated air
blowing out beneath a refrigerator. The work W is usually done by an electric
motor which compresses a fluid.
FIGURE (a) Typical refrigerator system. The
electric compressor motor forces a gas at high
pressure through a heat exchanger (condenser)
on the rear outside wall of the refrigerator where
Qh is given off and the gas cools to become
liquid. The liquid passes from a high-pressure
region, via a valve, to low-pressure tubes on the
inside walls of the refrigerator; the liquid
evaporates at this lower pressure and thus
absorbs heat from the inside of the refrigerator.
The fluid returns to the compressor where the
cycle begins again.
Figure on the left side shows a schematic diagram of an
impossible refrigerator or heat pump—that is, one that
absorbs energy Qc from a cold reservoir and expels an
equivalent amount of energy to a hot reservoir with zero
work done on the refrigerator; W = 0.

NOTE: It is impossible to construct a cyclical machine

whose sole effect is to transfer energy continuously by
heat from one object at lower temperature to another
object at a higher temperature without the input of
energy by work.
Refrigerators, Air Conditioners, and Heat Pumps

An ideal refrigerator would remove the most heat from the

interior while requiring the smallest amount of work. This ratio
is called the coefficient of performance, COP:

Typical refrigerators have COP values between 2 and 6.

Bigger is better!
Refrigerators, Air Conditioners, and Heat Pumps
An air-conditioner is essentially identical to a
refrigerator; the cold reservoir is the interior of
the house or other space being cooled, and the
hot reservoir is outdoors.
An air-conditioner takes heat QL from inside a
room or building at a low temperature, and
deposits heat QH outside to the environment at a
higher temperature.
Exhausting an air conditioner within the house
will result in the house becoming warmer, just as
keeping the refrigerator door open will result in
the kitchen becoming warmer.
Refrigerators, Air Conditioners, and Heat Pumps
A heat pump is the same as an
air conditioner, except with the
reservoirs reversed.
Heat is removed from the cold
reservoir outside, and exhausted
into the house, keeping it warm.
Note that the work the pump does
actually contributes to the desired
result (a warmer house) in this
case.
NOTE: Homes in summer are cooled using heat pumps called air
conditioners. The air conditioner transfers energy from the cool room
in the home to the warm air outside.
Refrigerators, Air Conditioners, and Heat Pumps
In an ideal heat pump with two operating temperatures (cold and
hot), the Carnot relationship holds; the work needed to add heat Qh
to a room is:

The COP for a heat pump:

Clausius statement of the second law of thermodynamics

In simpler terms, energy does not flow spontaneously from a cold object to
a hot object. For example, we cool homes in summer using heat pumps
called air conditioners. The air conditioner pumps energy from the cool
room in the home to the warm air outside. This direction of energy transfer
requires an input of energy to the air conditioner, which is supplied by the
electric power company.
Other Engine Types

• Two-stroke engines
• Diesel engines
• Rotary engines
• Turbine engines
• Steam engines
GASOLINE AND DIESEL ENGINES
In a gasoline engine, six processes occur in each cycle; five of these are
illustrated in Figure below.

Figure shows the four-stroke cycle of a conventional gasoline engine.

The Figure above shows a four-stroke cycle of a conventional gasoline engine
in which the piston moves up and down twice. This four-stroke cycle consists of
two upstrokes and two downstrokes:

(a)In the intake stroke, air is mixed with fuel.

(b)The intake valve is then closed, and the air–fuel mixture is compressed by
the piston.
(c)The mixture is ignited by the spark plug, with the result that the
temperature of the mixture increases.
(d)In the power stroke, the gas expands against the piston.
(e)Finally, the residual gases are expelled, and the cycle repeats.
Figure on left side shows a PV diagram for the
Otto cycle, which approximately represents the
processes occurring in an internal combustion
engine.

1. During the intake stroke O to A : the piston moves downward, and a gaseous mixture of
air and fuel is drawn into the cylinder at atmospheric pressure. In this process, the
volume increases from V2 to V1 . This is the energy input part of the cycle, as energy
enters the system (the interior of the cylinder) as internal energy stored in the fuel. This
is energy transfer by mass transfer—that is, the energy is carried with a substance.

2. During the compression stroke A to B: the piston moves upward, the air–fuel mixture is
compressed adiabatically from volume V1 to volume V2 , and the temperature increases
from TA to TB . The work done by the gas is negative, and its value is equal to the area
under the curve AB.
3. In process B to C, combustion occurs when the spark plug fires. This is not one of the strokes of the cycle because it
occurs in a very short period of time while the piston is at its highest position. The combustion represents a rapid
transformation from internal energy stored in chemical bonds in the fuel to internal energy associated with molecular
motion, which is related to temperature. During this time, the pressure and temperature in the cylinder increase rapidly,
with the temperature rising from TB to TC .

4. In the power stroke C to D: the gas expands adiabatically from V2 to V1 . This expansion causes the temperature to
drop from TC to TD . Work is done by the gas in pushing the piston downward, and the value of this work is equal to the
area under the curve CD.
5. In the process D to A: an exhaust valve is opened as the piston reaches the bottom of its travel, and the pressure
suddenly drops for a short time interval. During this interval, the piston is almost stationary and the volume is
approximately constant. Energy is expelled from the interior of the cylinder and continues to be expelled during the next
process.

6. In the final process, the exhaust stroke A to O: the piston moves upward while the exhaust valve remains open.
Residual gases are exhausted at atmospheric pressure, and the volume decreases from V 1 to V2 . The cycle then repeats.

If the air–fuel mixture is assumed to be an ideal gas, then the efficiency of the Otto cycle is

where ɣ is the ratio of the molar specific heats C P/CV for the fuel–air mixture and V1/V2 is the
compression ratio.
Entropy
A reversible engine has the following relation between the heat
transferred and the reservoir temperatures:

Rewriting,

This quantity, Q/T, is the same for both reservoirs, and is

defined as the change in entropy.
Entropy
 For this definition to be valid, the heat transfer must be
reversible.
 In a reversible heat engine, it can be shown that the
entropy does not change.
 A real engine will operate at a lower efficiency than a
reversible engine; this means that less heat is converted to
work. Therefore,

 Any irreversible process results in an increase of entropy.

Entropy
To generalize:
• The total entropy of the universe increases whenever an irreversible
process occurs.
• The total entropy of the universe is unchanged whenever a reversible
process occurs.
•Since all real processes are irreversible, the entropy of the universe
continually increases. If entropy decreases in a system due to work being
done on it, a greater increase in entropy occurs outside the system.
•As the total entropy of the universe increases, its ability to do work
decreases. The excess heat exhausted during an irreversible process
cannot be recovered; doing that would require a decrease in entropy,
which is not possible.
Order, Disorder, and Entropy
Entropy can be thought of as the increase in disorder in the universe. In
this diagram, the end state is less ordered than the initial state – the
separation between low and high temperature areas has been lost.
Order, Disorder, and Entropy
If we look at the ultimate fate of the universe in light of the continual increase in
entropy, we might envision a future in which the entire universe would have
come to the same temperature. At this point, it would no longer be possible to
do any work, nor would any type of life be possible. This is referred to as the
“heat death” of the universe.
So if entropy is continually increasing, how is life possible? How is it that
species can evolve into ever more complex forms? Doesn’t this violate the
second law of thermodynamics?
No – life and increasing complexity can exist because they use energy to
drive their functioning. The overall entropy of the universe is still
increasing. When a living entity stops using energy, it dies, and its
entropy can increase rather quickly.
END OF APPLIED THERMODYNAMICS