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Temperature and heat

Internal energy (U)


Is the energy associated with the microscopic components of a system (the
atoms and molecules of the system). The internal energy includes kinetic and
potential energy associated with the random translational, rotational, and
vibrational motion of the particles that make up the system, and any potential
energy bonding the particles together.

Heat (Q):
Is the transfer of energy between a system and its environment due to a
temperature difference between them.
Units of Heat
1- SI unit: Joule (J)
2- calorie (cal), where:
1 cal = 4.186 J
3- Calorie, with a capital C, used in describing the energy
content of foods, is actually a kilocalorie.
1 Cal = 1000 cal = 4186 J

SPECIFIC HEAT
If a quantity of energy Q is transferred to a substance of mass m, changing
its temperature by T = Tf - Ti , the specific heat c of the substance is
defined by:
(1)
SI unit: Joule per kilogram-degree Celsius ( J/kg . oC)

Dr. M. IBRAHIM

The quantity of energy required to raise the temperature of 1 kg of water by


1C is 4 186 J. Then cwater = 4186 J/kg . oC.
The quantity of energy required to raise the temperature of 1 kg of copper
by 1C is only 387 J. Then ccopper = 387 J/kg . oC.
From the definition of specific heat, we can express the energy Q needed to
change the temperature of a system of mass m by T as:
Q=mcT

(2)

Example:
The energy required to raise the temperature of 0.5 kg of water by 3 C is:
Q=mcT
Q = (0.5 kg) (4186 J/ kg C) (3C) = 6.28 x 10 3 J.
Note:
When the temperature increases, then Tf > Ti , then T is positive, hence Q
is positive as well. This means that thermal energy (heat) transfers into the
system.
When the temperature decreases, then Tf < Ti , then T is negative, hence Q
is negative as well. This means that thermal energy (heat) transfers out of
the system.
The table below shows the specific heat for some substances.

Dr. M. IBRAHIM

CALORIMETRY
One technique for measuring the specific heat of an object (solid or liquid) of
known mass mx, is to raise its temperature to some known temperature T x,
placing it in a vessel containing water of known mass m w and temperature Tw
(Tw < Tx), and measuring the final temperature of the water after equilibrium
has been reached, Tf . This technique is called calorimetry, and devices in
which this energy transfer occurs are called calorimeters (calorimeter is an
insulated vessel, so that energy doesnt leave it).

If the system of the sample and the water is isolated, the principle of
conservation of energy requires that the amount of energy Q hot that leaves
the object (of unknown specific heat) equal the amount of energy Q cold that
enters the water. Then:
Qcold + Q hot = 0
Qcold is positive because energy is flowing into cooler objects, and Q hot is
negative because energy is leaving the hot object. Then
mwcw(Tf - Tw) = mxcx(Tf - Tx)
If cw is known, then cx can be determined.
Example:
A 125-g block of an unknown substance with a temperature of 90.0 oC is
placed in a Styrofoam cup containing 0.326 kg of water at 20.0 oC. The
system reaches an equilibrium temperature of 22.4 oC. What is the specific
heat, cx, of the unknown substance if the heat capacity of the cup is
neglected?

Dr. M. IBRAHIM

Solution:

Latent Heat and Phase Change


A substance often undergoes a change in temperature when energy is
transferred between it and its surroundings. In some situations, however, the
transfer of energy does not result in a change in temperature. That is the
case whenever the substance changes its phase from one form to another.
Two common phase changes are; from solid to liquid (melting), from liquid to
gas (boiling).
All such phase changes involve a change in the system's internal energy but
no change in its temperature.
The energy Q needed to change the phase of a given pure substance is:

Q = mL

(3)

where L, called the latent heat of the substance, depends on the nature of
the phase change as well as on the substance. This parameter is called latent
heat (literally, the hidden heat) because this added or removed energy
does not result in a temperature change.
SI unit: The unit of latent heat is the joule per kilogram ( J/kg).
The latent heat of fusion Lf is used when a phase change occurs during
melting or freezing.
The latent heat of vaporization Lv is used when a phase change occurs during
boiling or condensing.

Dr. M. IBRAHIM

The positive sign in Equation (3) is used when energy enters a


system, causing melting or vaporization.
The negative sign corresponds to energy leaving a system, such
that the system freezes (goes from liquid to solid) or
condenses (goes from gas to liquid).

Melting and boiling


When a piece of ice (solid) is heated, its temperature begins to rise. When
the temperature reaches its melting point (0 C), the solid ice starts to
melt into liquid water. Although heating continues the temperature of the
ice water mixture remains constant until all the solid has melted. Once all
the ice has melted the temperature of water starts to rise until the liquid
water begins to boil at a temperature of 100 C. With continued heating the
temperature remains constant until all the liquid water has been converted
to steam (gas). The temperature then continues to rise as the gas is in a
closed container.

Dr. M. IBRAHIM

Then, when there is phase change, the temperature remains constant. The
heat supplied to the substance is needed for: (i) molecules to overcome
attractive forces from other molecules. (ii) separate molecules to greater
distances (increase the potential energy of molecules), (iii) breaking bonds.
The speed of molecules (and hence the average kinetic energy) doesnt
change since the temperature is constant.
Example:
Find the heat required to transfer a 1.00-g cube of ice at -30.0C into steam
(water vapor) at 120.0C.

Dr. M. IBRAHIM

The total amount of energy that must be added to change 1.00 g of ice at
-30.0C to steam at 120.0C is the sum of the results from all five parts of
the curve = 3.11 x 103 J.

ENERGY TRANSFER
Thermal energy (heat) flows spontaneously (by itself) from hotter to colder
bodies, never the other way round. Heat continues to transfer from the
hotter body to the colder body until both bodies have the same temperature.

Dr. M. IBRAHIM

When this happens, the two bodies are said to be in thermal equilibrium.
Thermal energy is transferred by heat between a system and its
surroundings by three processes: thermal conduction, convection, and
radiation.
Thermal Conduction
Conduction is the flow of heat along matter without any flow of matter.
For heat to flow by conduction from one body to another, the two bodies
must be in contact.

Conduction is explained by means of the kinetic molecular theory. The fastmoving molecules in the hotter parts of matter collide with the slower-moving
molecules in the colder parts in contact with them, thus, passing on to them a
part of their kinetic energy. Therefore, kinetic energy travels across
molecule to molecule.
Metals are best conductors of heat because they have many free electrons
that are free to move throughout the body of the metal. If part of the
metallic object is hotter than another, free-moving fast electrons move
across the body of the metal, and thus carry thermal energy across the body,
much faster than it can be transferred from molecule to molecule by
molecular collision. Therefore metals are better conductors than non-metallic
solids.
Silver and copper are the best conductors of thermal energy. Water, glass,
air, plastic and wood are poor conductors of heat. Poor conductors of heat
are called insulators.
Consider a slab of material of thickness L and cross-sectional area A with its
opposite faces at different temperatures Tc and Th, where Th > Tc.
The slab allows energy to transfer from the region of higher temperature to
the region of lower temperature by thermal conduction.

Dr. M. IBRAHIM

The rate of energy transfer, H = Q/t, is proportional to the cross-sectional


area (A) of the slab and the temperature difference (T = T h - Tc) and is
inversely proportional to the thickness of the slab (L):

where k, a proportionality constant that depends on the material, is called


the thermal conductivity. Substances that are good conductors have large
thermal conductivities, whereas good insulators have low thermal
conductivities.

Dr. M. IBRAHIM

Example: Find the energy transferred in 1.00 h by conduction through a


concrete wall 2.0 m high, 3.65 m long, and 0.20 m thick if one side of the wall
is held at 20C and the other side is at 5C.

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Convection
In fluids (liquids and gases) heat transfers partly by conduction, but more
importantly by a natural stirring phenomenon called convection.
Convection is the flow of heat through a fluid from places of higher
temperature to places of lower temperature by the movement of the fluid
itself.
When a quantity of fluid is heated it expands i.e. its volume increases. Its
mass, however remains constant, hence its density (density = mass/volume)
decreases, hence it tends to float upward. Other denser parts of the fluid
sink, thus moving downward. The result is that upward, downward and lateral
currents of fluid movement are created. These currents are called convection
currents.

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Convection examples:

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Radiation
Radiation is the transfer of heat energy in the form of an infra-red
radiation (waves) that is a part of electromagnetic spectrum.

The radiation of heat occurs from any hot body. Heat radiation travels in all
directions from a hot source with the speed of light 3x108 m/s.

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Dark dull surfaces are good emitters and good absorbers of heat
radiation.
Bright shiny surfaces are poor emitters AND poor absorbers of heat
radiation.

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Thermal Expansion of Solids and Liquids


As the temperature of a substance increases, its volume increases. This
phenomenon is known as thermal expansion. Thermal expansion is a
consequence of the change in the average separation between the atoms in an
object. Taking solids as an example, as the temperature of the solid
increases, the atoms oscillate with greater amplitudes; as a result, the
average separation between them increases. Consequently, the object
expands.
Because the linear dimensions of an object change with
temperature, it follows that surface area and volume change as well.
Suppose an object that has an initial length L o at some initial temperature To.
If its temperature increases to a final temperature T, its length increases to
a final length L. The increase in length L = L-Lo is given by:

where T = T-To and the proportionality constant is called the coefficient


of linear expansion for a given material and has units of (oC)-1.

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Example:
A steel railroad track has a length of 30.0 m when the temperature is 0 oC.
What is its length on a hot day when the temperature is 40.0 oC?
Solution:

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(a) A bimetallic strip bends as the


temperature changes because the two
metals
have
different
expansion
coefficients.
(b) A bimetallic strip used in a thermostat
to break or make electrical contact.

Macroscopic Description of an Ideal Gas


An ideal gas is a collection of atoms or molecules that move randomly and
exert no long-range forces on each other. Each particle of the ideal gas is
individually pointlike, occupying a negligible volume.
A gas usually consists of a very large number of particles, so its convenient
to express the amount of gas in a given volume in terms of the number of
moles, n. One mole of any substance is that amount of the substance that
contains Avogadros number NA = 6.02 x 1023 of constituent particles (atoms
or molecules).

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The number of moles n of a substance is related to its mass m through the


expression:

where M is the molar mass of the substance (the molar mass of the
substance is defined as the mass of one mole of that substance, usually
expressed in grams per mole).
Note:
It turns out that Avogadros number was chosen so that the mass in grams of
one Avogadros number of an element is numerically the same as the mass of
one atom of the element, expressed in atomic mass units (u).
This relationship is very convenient. Looking at the periodic table of the
elements, we find that carbon has an atomic mass of 12 u, so, the molar mass
of carbon M = 12 g and 12 g of carbon consists of exactly 6.02 x 10 23 atoms
of carbon. The atomic mass of oxygen is 16 u, so in 16 g of oxygen there are
again 6.02 x 1023 atoms of oxygen.
The pressure P (Pa), volume V (m3), temperature T (K), and amount n of an
ideal gas in a container are related to each other by an equation of state:

PV = nRT

This expression is known as the ideal gas law.


R is called the universal gas constant. In SI units, where pressure is
expressed in pascals and volume in cubic meters, R = 8.31 J/mol.K.
The ideal gas law is often expressed in terms of the total number of
molecules N. Because the number of moles n equals the ratio of the total
number of molecules N and Avogadros number NA, (n = N/NA), we can write
ideal gas law as:

Notes:

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1- T (K) = T ( C) + 273.

-3

2- V (in liters: L) = 10 m .
3- The pressure of a gas is explained by the particles colliding with the
sides of the container (constant volume), in doing so they exert a
force, and hence a pressure.
Example:
An ideal gas at 20.0 oC and a pressure of 1.50 x 10 5 Pa is in a container having
a volume of 1.00 L. (a) Determine the number of moles of gas in the container.
(b) The gas pushes against a piston, expanding to twice its original volume,
while the pressure falls to atmospheric pressure. Find the final temperature
of the gas.
Solution:
(a)

(b)

Then:

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The Kinetic Theory of Gases


The kinetic theory of gases model makes the following assumptions:
1. The number of molecules in the gas is large, and the average separation
between them is large compared with their dimensions.
2. The molecules obey Newtons 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, with a wide distribution of speeds.
3. The molecules interact only through short-range forces during elastic
collisions.
4. The molecules make elastic collisions with the walls.
5. All molecules in the gas are identical.
The average translational kinetic energy Kavg of a molecule of mass moving
at an average speed
in a gas of temperature T is given by:

This means that the temperature of a gas is a direct measure of the average
molecular kinetic energy of the gas. As the temperature of a gas increases,
the molecules move with higher average kinetic energy.
The total translational kinetic energy of N molecules of gas is simply N times
the average energy per molecule:

Since the mass of the gas m that has N molecules each of mass is: m = N,
then:

From this result, we see that the total translational kinetic energy of a
system of molecules is proportional to the absolute temperature of the
system.

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If the temperature of the gas in the container increases, then the particles
gain kinetic energy and will move faster and collide with the side more
frequently and hit the walls harder, therefore exert a greater pressure.
For a monatomic gas, translational kinetic energy is the only type of energy
the molecules can have, so the internal energy U for a monatomic gas:

The square root of


molecules

vrms given by:

is called the root-mean-square (rms) speed of the

where M is the molar mass in kilograms per mole.


This equation shows that, at a given temperature, lighter molecules tend to
move faster than heavier molecules.
For example, if gas in a vessel consists of a mixture of hydrogen and oxygen,
the hydrogen (H2) molecules, with a molar mass of 2.0 x 10 -3 kg/mol, move
four times faster than the oxygen (O 2) molecules, with molar mass 32 x 10 -3
kg/mol. If we calculate the rms speed for hydrogen at room temperature
(300 K), we find

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The Laws of Thermodynamics


Energy can be transferred to a system by heat and by work done on the
system.
Consider a gas contained by a cylinder fitted with a movable piston and in
equilibrium. The gas occupies a volume V and exerts a uniform pressure P on
the cylinder walls and the piston. The gas is compressed slowly enough so the
system remains essentially in thermodynamic equilibrium at all times. As the
piston is pushed downward by an external force F through a distance y, the
work done on the gas is (Note that F = PA and V = A y).

W = - F y = - PA y

The work W done on a gas at constant pressure is given by:

W = - P V
Where P is the pressure throughout the gas and V (Vf Vi) is the change in
volume of the gas during the process.

If the gas is compressed, V is negative (Vf < Vi) and the work done on the
gas is positive. If the gas expands, V is positive (Vf > Vi) and the work done
on the gas is negative. If V doesnt change (Vf = Vi), the work is zero.

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A process in which the pressure


remains constant is called an
isobaric process.
The pressure vs. volume graph, or
PV diagram, of an isobaric
process is shown in the figure.

The PV diagram for a gas being


compressed at constant pressure.
The shaded area represents the
work done on the gas.
The curve on such a graph is called the path taken between the initial and
final states, with the arrow indicating the direction the process is going, in
this case from smaller to larger volume. The area under the graph is:

Area = P (Vf Vi) = P V

The work done on the gas equals the negative of the area under the
graph in a PV diagram.
Example:

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Quick Quiz
By visual inspection, order the PV diagrams shown below from the most
negative work done on the system to the most positive work done on the
system.
(a)a,b,c,d (b) a,c,b,d (c) d,b,c,a (d) d,a,c,b

Notice that the graphs in the above figure all have the same starting and
endpoints, but the areas beneath the curves are different. The work done
on a system depends on the path taken in the PV diagram.
EXAMPLE
Find the work done on the gas in Figures a and b above.

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THE FIRST LAW OF THERMODYNAMICS


If a system undergoes a change from an initial state to a final state, where Q
is the energy transferred to the system by heat and W is the work done on
the system, the change in the internal energy of the system, U, is given by:
U = Uf - Ui = Q + W
The quantity Q is positive when energy is transferred into the gas by heat
and negative when energy is transferred out of the gas by heat. The quantity
W is positive when work is done on the gas and negative when work is done
by the gas on its environment.
There are four basic types of thermal processes, which will be studied and
illustrated by their effect on an ideal gas.

Isobaric Processes
In an isobaric process the pressure remains constant as the gas expands or is
compressed.

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Isobaric expansion

Isobaric compression

Adiabatic Processes
In an adiabatic process, no energy enters or leaves the system by heat. Such
a system is insulatedthermally isolated from its environment. In general,
however, the system isnt mechanically isolated, so it can still do work. A
sufficiently rapid process may be considered approximately adiabatic because
there isnt time for any significant transfer of energy by heat.
For adiabatic processes Q = 0, so the first law becomes:

Isovolumetric Processes

U = W

An isovolumetric process, sometimes called an isochoric process, proceeds at


constant volume, corresponding to vertical lines in a PV diagram. If the
volume doesnt change, no work is done on or by the system, so W = 0, and the
first law of thermodynamics reads:
U = Q
This result tells us that in an isovolumetric process, the change in internal
energy of a system equals the energy transferred to the system by heat.

Isothermal Processes
During an isothermal process, the temperature of a system doesnt change. In
an ideal gas the internal energy U depends only on the temperature, so it

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follows that U = 0 because T = 0. In this case, the first law of


thermodynamics gives:
W=-Q
A plot of P versus V at constant temperature for an ideal gas yields a
hyperbolic curve called an isotherm.

Isobaric expansion

Isobaric compression

Cyclic Processes
During a cyclic process, the gas starts at some state and returns back to it.
Then Ui = Uf, so it follows that U = 0. In this case, the first law of
thermodynamics gives:
W=-Q

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The magnitude of the work done in a cyclic process equals the area enclosed
by the cycle.
Example:

The work done during one cycle (A-B C A)


is given by the area enclosed by the cycle:
area = 0.5 x 4 x (6x103) = 12x103 J
Then Work = - 12x103 J. (because the gas is
expanding).

Example:
A quantity of 4.00 moles of a monatomic
ideal gas expands from an initial volume of
0.100 m3 to a final volume of 0.300 m3 and
pressure of 2.5 x 105 Pa as shown. Compute
(a) the work done on the gas, (b) the
change in internal energy of the gas, and
(c) the thermal energy transferred to the
gas.
Solution
(a)

Find the work done on the gas by computing the area under the
curve:

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The gas is expanding, so the work done on the gas is negative.


(b)

(c)

HEAT ENGINES AND


THERMODYNAMICS

THE

SECOND

LAW

OF

A heat engine takes in energy by heat and partially converts it to other


forms, such as electrical and mechanical energy. For example, in the internal
combustion engine in an automobile, energy enters the engine as fuel is
injected into the cylinder and combusted, and a fraction of this energy is
converted to mechanical energy.
In general, a heat engine carries some working substance (gas for example)
through a cyclic process during which (1) energy is transferred by heat from a
source at a high temperature, (2) work is done by the engine, and (3) energy is
expelled by the engine by heat to a source at lower temperature.
The engine absorbs energy Qh from the hot reservoir, does work Weng, then
gives up energy QC to the cold reservoir. (Note that negative work is done on
the engine, so that W = -Weng.)
Because the working substance goes through a cycle, always returning to its
initial thermodynamic state, its initial and final internal energies are equal, so
U = 0. From the first law of thermodynamics, therefore,

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U = 0 = Q + W then Qnet = - W = Weng. Then the work Weng done by a heat


engine equals the net energy Qnet absorbed by the engine.

Since Qnet = |Qh| - |Qc|, therefore,


Weng = |Qh| - |Qc|

The thermal efficiency e of a heat engine is defined as the work done by the
engine, Weng, divided by the energy absorbed during one cycle, Qh:

Example:
During one cycle, an engine extracts 2.00 x 10 3 J of energy from a hot
reservoir and transfers 1.50 x 103 J to a cold reservoir. (a) Find the thermal
efficiency of the engine. (b) How much work does this engine do in one cycle?

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(c) How much power does the engine generate if it goes through four cycles
in 2.50 s?
Solution
(a)

(b)

(c)

The Second Law of Thermodynamics


It is impossible to construct a heat engine that, operating in a cycle,
produces no effect other than the input of energy by heat 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, Weng can never be equal to |Q h| or, alternatively, that some energy |
Qc| must be rejected to the environment.

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The Carnot Engine


In 1824, a French engineer named Sadi Carnot described a theoretical engine,
now called a Carnot engine. He showed that a heat engine operating in an
ideal, reversible cyclecalled a Carnot cyclebetween two energy reservoirs
is the most efficient engine possible. Such an ideal engine establishes an
upper limit on the efficiencies of all other engines. Carnots theorem can be
stated as follows:
No real heat engine operating between two energy reservoirs can be more
efficient than a Carnot engine operating between the same two reservoirs.
The Carnot cycle consists of two adiabatic processes and two isothermal
processes.

For a Carnot engine, the following relationship between the thermal energy
transfers and the absolute temperatures can be derived:

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The thermal efficiency of the engine is given by:

Hence, the thermal efficiency of a Carnot engine is

Example:
A steam engine has a boiler that operates at 500 K. The energy from the
boiler changes water to steam, which drives the piston. The temperature of
the exhaust is that of the outside air, 300 K. (a) What is the maximum
possible engines efficiency? (b) If a 3.50 x 103 J of energy is supplied from
the boiler, find the work done by the engine on its environment.
Solution
(a)

(b)

ENTROPY
Studies showed that isolated systems tend toward disorder, and entropy S is
a measure of this disorder. For example, if you could view gas molecules, you

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would see that they move haphazardly in all directions, bumping into one
another, changing speed upon collision, some going fast and others going
slowly. This situation is highly disordered.
Let Q be the energy absorbed or expelled during a reversible, constant
temperature process between two equilibrium states. Then the change in
entropy during any constant temperature process connecting the two
equilibrium states is defined as:

SI unit: joules/kelvin ( J/K).


Example:
Find the change in entropy of 3.00 x 10 2 g of lead when it melts at 327 oC.
Lead has a latent heat of fusion of 2.45 x 10 4 J/kg.
Solution

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Past AP Papers

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2008

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