Thermal Physics (temperature, ideal gases, thermodynamics)

Internal energy
• It is the energy of atoms
• Atoms possess K.E (due to motions) and P.E (due to intermolecular forces)
• I.E= sum of K.E + sum of P.E
So, internal energy is the microscopic sum of kinetic energies and potential
energies of molecules; these energies are randomly distributed

Temperature
• Degree of hotness or coldness and it is directly proportional to avg (mean)
kinetic energy of molecules

Heat energy
• The energy that transfers from one body to another due to temperature
difference
• Heat transfer in leads to increase in I.E and vice versa
• Normally the heat transfers from hot body to cold body

There are four processes of heat transfer:

1. Conduction
2. Convection
3. Radiation
4. Evaporation

Thermal equilibrium • The bodies will be in

thermal equilibrium if their
A B temperatures are same

TA TB

• The rate of heat flow depends on temperature difference:

Larger the temperature difference, higher the rate of flow of heat

• Heat transfer from A to B = heat transfer from B to A

Zeroth law of thermodynamics
• If body A and body B are in thermal equilibrium, similarly the body B and body
C are in thermal equilibrium then body A and body C will me in thermal
equilibrium

Temperature
Thermometer: a thermometer must have:
1. Thermometric property
2. Two fixed point
3. Scale

Two fixed points

• Fixed points act as a reference temperature
• The lower fixed point is the melting point of ice that is 0˚C and upper fixed
point is boiling point of water that is 100˚C

Scale
• No. of divisions b/w upper and lower fixed point

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Thermometric property
• Any physical property that changes with temperature
• The change maybe direct or inverse but it should be measurable and
reproducible
• The change in thermometric property must be one sided that is it should
either only increase or decrease
• The change in thermometric property may not be linear with temperature but
linear changes give accurate temperature
• We assume that thermometric properties vary linearly with temperature

△T.P ∝ △T At lower fixed point

θ/100 = Xθ -X0/ X100 – X0 Temperature= T0 T.P= X0
At upper fixed point
where: Temperature= T100 T.P=X100
θ = unknown temperature At any other temperature
100= difference b/w upper and lower Temperature= Tθ T.P=X θ
Fixed point

Liquid in Glass thermometer

• Length of liquid in bore varies with temperature
• Suitable for measuring temperature from 0 to 100
• For liquid in glass thermometer:
θ/100 = lθ -l0/ l100 – l0

Advantages Disadvantages
• Portable • Small range
• Less expensive • Larger heat capacity so not suitable for
measuring temperature of small quantities

• Easy to use • Not suitable to measure rapid changes in

temperature

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Thermocouple thermometer
• Consist of a voltmeter and have two wires made of
different materials with different
conductivities
• Voltage varies with temperature

How to calibrate
• One junction is kept at a fixed temperature
and the other junction is immersed turn by
turn in pure melting ice, boiling water and in
unknown temperature
• We record the voltmeter and use the
formula below to find the calibration

θ/100= Eθ -E0/ E100 – E0

Advantages Disadvantages
• Wide range • Not portable
• Very fast and responsive • expensive
• Smaller heat capacity

Thermistor Resistance
• Thermistor is a type of resistor whose
resistance varies with changes in temperature
• resistance changes rapidly over a narrow range of
temperatures
• As a thermistor gets hotter, its
resistance decreases so inverse
relationship
• This means a thermometer based on a thermistor
can be used to measure a range of temperatures

4
 Calibration
• Set up a circuit with a power source, a fixed resistor, a thermistor, and an
ohmmeter
• Set up a Bunsen burner, tripod, gauze, beaker with ice, stirring rod, and
waterproof thermistor
• Three different set ups pure melting ice, boiling water and in unknown
temperature
• Allow time for the temperature to reach equilibrium, stir the water, and
ensure the thermometer bulb is completely submerged in the water and level
with the thermistor
• Measure the resistance using the ohmmeter and use the formula below to find
the calibration
θ/100= Rθ -R0/ R100 – R0

Advantages Disadvantages
• Wide range • Not portable
• Very fast and responsive • expensive
• Smaller heat capacity

Constant volume gas thermometer

• Pressure varies with temperature
• The flask is placed in pure melting
ice, boiling water and unknown
temperature and the change in the
mercury level is measured
• P0=ρgho+ATM to find the pressure

θ/100= Pθ -P0/ P100 – P0

Advantages Disadvantages
• Wide range • High heat capacity
• Very accurate (used to calibrate • Less responsive
other thermometers)

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Empirical scale of temperature

• θ/100 = Xθ -X0/ X100 – X0

• We assume that T.P varies linearly with temperature
• Not as accurate
o The freezing and boiling point of water will actually change as its pressure
changes
• The Celsius scale is used to measure the temperature in a liquid-in-glass
thermometer
o However, the expansion of the liquid might be non-linear

So, we make a new scale that is more accurate aka thermodynamic scale which
will be based on ideal gas laws

Thermodynamic scale
• The Kelvin scale is known as the thermodynamic scale and was designed to
overcome the problem with scales of temperature
• The thermodynamic scale is said to be an absolute scale that is not defined in
terms of a property of any particular substance
• will be based on ideal gas laws
• Fixed point is triple point of water which is more accurately achievable
more accurate

θ/273.15= PVθ / PVTR

Absolute Zero
• On the thermodynamic (Kelvin) temperature scale, absolute zero is defined as:
The lowest temperature possible. Equal to 0 K or -273.15 °C
• Also known as triple point of water
TTR = 273.15 K
• It is the fixed temperature at which three states of matter i.e. solid, liquid
and gas are in thermal equilibrium
• The formula of thermodynamic scale and empirical formula is the same

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Ideal gas
• Imaginary gas that obeys all the gas laws at all temperatures, pressures and
volume
• An ideal gas is one which obeys the relation pV ∝ T
Where:
1. p = pressure of the gas (Pa)
2. V = volume of the gas (m3)
3. T = thermodynamic temperature (K)

Kinetic molecular theory for ideal gas

• Consist of large no. of molecules moving
randomly
• Molecules behave like small, elastic, rigid
spheres
• Size of molecule is negligible as size
compared to size of container
• No intermolecular forces that is molecules
exert. No force on each other except during
collisions
• Molecules collide with each other and the walls of the container elastically
• Ideal gases exert pressure on walls of container due to these repeated
collisions
• The collision time is negligible as compared to the time interval between each
collision
The pressure exerted by ideal gas on the walls of container is due to molecular
bombardment

This pressure can be increased:

Increasing no. of collisions Increasing the force of collision

1. Increase the no. of molecules 1. changing the temperature

2. Reduce the volume
3. changing the temperature

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Gas Laws

Boyle’s Law
• If the temperature T is constant, then Boyle’s Law is given by:

• This leads to the relationship between the pressure and volume for a fixed
mass of gas at constant temperature:

P1V1 = P2V2

Graphs

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Q. why on increasing the external pressure the volume decreases
Ans. Pressure increases so the spaces between the molecules decreases which
causes the molecules to comes closer, decreasing the volume

Q. why on decreasing the volume the internal pressure increases

Ans. When the volume decreases, the number of collisions will increase so the
pressure increases

Charles's Law
• If the pressure P is constant, then Charles’s law is given by:
V∝T

• This leads to the relationship between the volume and thermodynamic

temperature for a fixed mass of gas at constant pressure:

Explanation
When the temperature increases,
the internal energy will increase
due to which the kinetic energy and
their speed will increase. Molecules
collide forcefully and collide with
piston making it move upwards;
volume increases

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Pressure Law
• Pressure of fixed mass of gas is directly proportional to absolute temperature
provides that volume stays constant
• if the volume V is constant, the the Pressure law is given by:
P∝T

• This leads to the relationship between the pressure and thermodynamic

temperature for a fixed mass of gas at constant volume:

(temp should be in K)

PV = Const Boyles law %#

= Const
$
#
= Const Charles law %#
$ so, = nR where:
$
%
= Const Pressure law
$ n= no. of moles

R= molar gas const

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The Boltzmann Constant
• The Boltzmann constant k is used in the ideal gas equation and is defined
by the equation:

• Where:
o R = molar gas constant
o NA = Avogadro’s constant
• Boltzmann’s constant therefore has a value of

• The Boltzmann constant relates the properties of microscopic particles (e.g.

kinetic energy of gas molecules) to their macroscopic properties (e.g.
temperature)
o This is why the units are J K-1
• Its value is very small because the increase in kinetic energy of a molecule is
very small for every incremental increase in temperature
•
Assumptions of the Kinetic Theory of Gases
• Gases consist of atoms or molecules randomly moving around at high speeds
• The kinetic theory of gases models the thermodynamic behavior of gases by
linking the microscopic properties of particles (mass and speed)
to macroscopic properties of particles (pressure and volume)

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• The theory is based on a set of the following assumptions:
o Molecules of gas behave as identical, hard, perfectly elastic spheres
o The volume of the molecules is negligible compared to the volume of the
container
o The time of a collision is negligible compared to the time between
collisions
o There are no forces of attraction or repulsion between the molecules
o The molecules are in continuous random motion
• The number of molecules of gas in a container is very large, therefore
the average behavior (eg. speed) is usually considered

Derivation of the Kinetic Theory of Gases Equation

• When molecules rebound from a wall in a container, the change in momentum

gives rise to a force exerted by the particle on the wall
• Many molecules moving in random motion exert forces on the walls which
create an average overall pressure, since pressure is the force per unit area
• Picture a single molecule in a cube-shaped box with sides of equal length l
• The molecule has a mass m and moves with speed c, parallel to one side of the
box
• It collides at regular intervals with the ends of the box, exerting a force and
contributing to the pressure of the gas
• By calculating the pressure this one molecule exerts on one end of the box, the
total pressure produced by all the molecules can be deduced
•
•

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5 Step Derivation
1. Find the change in momentum as a single molecule hits a wall
perpendicularly
• One assumption of the kinetic theory is that molecules rebound elastically
• This means there is no kinetic energy lost in the collision
• If they rebound in the opposite direction to their initial velocity, their final
velocity is -c
• The change in momentum is therefore:
• Δp = −mc − (+mc) = −mc − mc = −2mc
2. Calculate the number of collisions per second by the molecule on a wall
• The time between collisions of the molecule travelling to one wall and back is
calculated by travelling a distance of 2l with speed c:

• Note: c is not taken as the speed of light in this scenario

3. Find the change in momentum per second
• The force the molecule exerts on one wall is found using Newton’s second law
of motion:

• The change in momentum is +2mc since the force on the molecule from the
wall is in the opposite direction to its change in momentum
4. Calculate the total pressure from N molecules
• The area of one wall is l2
• The pressure is defined using the force and area:

• This is the pressure exerted from one molecule

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• To account for the large number of N molecules, the pressure can now be
written as:

• Each molecule has a different velocity and they all contribute to the pressure
• The mean squared speed of c2 is written with left and right-angled brackets
<c2>
• The pressure is now defined as:

5. Consider the effect of the molecule moving in 3D space

• The pressure equation still assumes all the molecules are travelling in the same
direction and colliding with the same pair of opposite faces of the cube
• In reality, all molecules will be moving in three dimensions equally
• Splitting the velocity into its components cx, cy and cz to denote the amount in
the x, y and z directions, c2 can be defined using Pythagoras’ theorem in 3D:
• c2 = cx2 + cy2 + cz2
• Since there is nothing special about any particular direction, it can be
determined that:
• <cx2> = <cy2> = <cz2>
• Therefore, <cx2> can be defined as:

• The box is a cube and all the sides are of length l

• This means l3 is equal to the volume of the cube, V
• Substituting the new values for <c2> and l3 back into the pressure equation
obtains the final equation:

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• This is known as the Kinetic Theory of Gases equation

•
• This can also be written using the density ρ of the gas:

• Rearranging the pressure equation for p and substituting the density ρ:

Root-Mean-Square Speed

• To calculate the average speed of the particles in a gas, take the square root of
the mean square speed:

There are two methods:

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• cr.m.s is known as the root-mean-square speed and still has the units of m s-1
• The mean square speed is not the same as the mean speed

Average Kinetic Energy of a Molecule

• An important property of molecules in a gas is their average kinetic energy

• This can be deduced from the ideal gas equations relating pressure, volume,
temperature and speed
• Recall the ideal gas equation: pV = NkT
• Also recall the equation linking pressure and mean square speed of the
molecules:

• The left-hand side of both equations are equal (pV)

• This means the right-hand sides are also equal:

• N will cancel out on both sides and multiplying by 3 obtains the equation:
• m<c2> = 3kT
• Recall the familiar kinetic energy equation from mechanics:

• Instead of v2 for the velocity of one particle, <c2> is the average speed of all
molecules
• Multiplying both sides of the equation by ½ obtains the average translational
kinetic energy of the molecules of an ideal gas:

• Where:

o EK = kinetic energy of a molecule (J)

o m = mass of one molecule (kg)

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 o <c2> = mean square speed of a molecule (m2 s-2)
o k = Boltzmann constant
o T = temperature of the gas (K)

• Note: this is the average kinetic energy for only one molecule of the gas

Q. a) there are 2 moles of ideal gas at room temperature (25˚C) in a closed

container.

Find:

i) mean kinetic energy

sol:

= 1.5 x (1.38 x 10-2) x (298)

=6.16 x 10-21J

ii) internal energy

sol:
I.E= sum of K.E + sum of P.E
• The P.E will be zero because no intermolecular forces in ideal gases
I.E= N <K.E> (N is no. of molecules)
2 x 6.02 x 1023 (6.16 x 10-21)

b) Another container B contains 2 moles of real gas at room temperature (25˚C)

Compare the mean kinetic energy
Ans. Same mean kinetic energy because they are at the same temperature (25˚C)
Vrms ∝ √𝐓
𝐕𝟏 𝐕𝟐
=
√𝑻𝟏 √𝑻𝟐

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Heat capacity
• To increase temperature, heat must be added
Q ∝ ∆T
Q = C∆T Where C = heat capacity
𝐐
So, C =
∆𝐓

• Heat capacity is the heat transfer per unit change in temperature

• It is the amount of heat transferred to change the temperature of a body by one
Kelvin
• Unit = JK-1
.
• C∝
∆$

• Depends on mass, smaller the mass, smaller the heat capacity

Specific heat capacity

Q ∝ m and Q ∝ ∆T
Where C = heat capacity
Combining them will give Q ∝ m∆T
So, Q = mC∆T
• The amount of heat transferred peer unit mass per unit change in temperature
• amount of heat required by one kg of mass to change its temperature by one
Kelvin

molar heat capacity

the amount of heat required per mole per unit change in temperature
Q = nC∆T
Where n= no. of moles

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Low v high specific heat capacity
• If a substance has
a low specific heat
capacity, it heats up and
cools down quickly
• If a substance has
a high specific heat
capacity, it heats up and
cools down slowly
• The specific heat
capacity of different
substances determines
how useful they would
be for a specific purpose
eg. choosing the best material for kitchen appliances

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Latent heat
• Latent means hidden
• When a substance changes state, there is no temperature change
• The energy supplied to change the state is called the latent heat and is defined
as:

The thermal energy / amount of heat required to change the state of 1 kg of

mass of a substance without any change of temperature

• Latent heat doesn’t change the K.E of the molecules as the temperature stays
constant
• It changes the P.E of molecules as intermolecular forces change
• When latent heat is added, the intermolecular forces weakens as bond
breaking is endothermic
• When latent heat is withdrawn, the intermolecular forces strengthen e.g.
freezing or condensing since bond formation is exothermic

Q ∝ m where Q is latent heat

Q = mL where L is specific latent heat

𝐐
So, L=
𝐌

Specific latent heat: amount of heat required per unit mass to change the state at
a constant temperature
There are two types of specific latent heat:
Specific latent heat of fusion (melting) Specific latent heat of vaporization (boiling)
• The thermal energy required to • The thermal energy required to convert 1
convert 1 kg of solid to liquid with no kg of liquid to gas with no change in
change in temperature temperature
• this is used when melting a solid or • This is used when vaporizing a liquid or
freezing a liquid condensing a gas

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 Heating and cooling curve
• Crushed ice at -10 is heated at a constant rate and temperature is measured
at fixed intervals of time
• A graph is plotted temperature against time, known as heating curve

LHV > LHF

• AS WE CAN SEE FROM THE GRAPH: less energy is required to melt then to boil
• This is due to the reason that in melting the change in volume is n egligible so
no work should be done against atmosphere. When liquid turns into gas its
volume increases 1600 times so work has to be done against atmosphere to
increase this volume
WD = P∆V
Specific heat capacity is related to gradient: smaller the gradient larger the
heat capacity

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 Law of heat exchange
Heat lost = heat gained

Q1 block = Q2 water
(mc∆T) = (mc∆T)
0.8 x 500 (90 – x) = 0.5 x 4200 x (x – 1)
X = 22.8˚C

Work Done by a Gas

• When a gas expands, it does work on its surroundings by exerting pressure on

the walls of the container it's in
• This is important, for example, in a steam engine where expanding steam
pushes a piston to turn the engine
• The work done when a volume of gas changes at constant pressure is defined
as: W = pΔV
• Where:
o W = work done (J)
o p = external pressure (Pa)
o V = volume of gas (m3)

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• For a gas inside a cylinder enclosed by a moveable piston, the force exerted by
the gas pushes the piston outwards
• Therefore, the gas does work on the piston

• The gas expansion pushes the piston a distance s

Derivation
• The volume of gas is at constant pressure. This means the force F exerted by
the gas on the piston is equal to : F = p × A
• Where:
o p = pressure of the gas (Pa)
o A = cross-sectional area of the cylinder (m2)
• The definition of work done is: W = F × s
• Where:
o F = force (N)
o s = displacement in the direction of force (m)

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• The displacement of the gas d multiplied by the cross-sectional area A is the
increase in volume ΔV of the gas:

• W=p×A×s
• This gives the equation for the work done when the volume of a gas changes
at constant pressure: W = pΔV
• Where:
o ΔV = increase in the volume of the gas in the piston when expanding
(m3)
• This is assuming that the surrounding pressure p does not change as the gas
expands
• This will be true if the gas is expanding against the pressure of the
atmosphere, which changes very slowly
• When the gas expands (V increases), work is done by the gas
• When the gas is compressed (V decreases), work is done on the gas

Q. When a balloon is inflated, its rubber walls push against the air around it.
Calculate the work done when the balloon is blown up from 0.015 m3 to 0.030
m3.Atmospheric pressure = 1.0 × 105 Pa.

• Step 1: Write down the equation for the work done by a gas
• W = pΔV
• Step 2: Substitute in values

ΔV = final volume − initial volume = 0.030 − 0.015 = 0.015 m3

• W = (1.0 × 105) × 0.015 = 1500 J

Exam Tip

The pressure p in the work done by a gas equation is not the pressure of the gas
but the pressure of the surroundings. This is because when a gas expands, it does
work on the surroundings.

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The First Law of Thermodynamics

• The first law of thermodynamics is based on the principle of conservation of

energy
• When energy is put into a gas by heating it or doing work on it, its internal
energy must increase:

• The increase in internal energy = Energy supplied by heating + Work done on

the system
• The first law of thermodynamics is therefore defined as: ΔU = q + W
• Where:
o ΔU = increase in internal energy (J)
o q = energy supplied to the system by heating (J)
o W = work done on the system (J)
• The first law of thermodynamics applies to all situations, not just for gases
o There is an important sign convention used for this equation
• A positive value for internal energy (+ΔU) means:
o The internal energy ΔU increases
o Heat q is added to the system
o Work W is done on the system (or by a gas)
• A negative value for internal energy (−ΔU) means:
o The internal energy ΔU decreases
o Heat q is taken away from the system
o Work W is done by the system (or on a gas)
• This is important when thinking about the expansion or compression of a gas
• When the gas expands, it transfers some energy (does work) to its
surroundings
• This decreases the overall energy of the gas

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• Therefore, when the gas expands, work is done by the gas (−W)

• When a gas expands, work done W is negative

• When the gas is compressed, work is done on the gas (+W)

• When a gas is compressed, work done W is positive

• Positive or negative work done depends on whether the gas is compressed or

expanded

Graphs of Constant Pressure & Volume

• Graphs of pressure p against volume V can provide information about the
work done and internal energy of the gas
o The work done is represented by the area under the line
• A constant pressure process is represented as a horizontal line
o If the volume is increasing (expansion), work is done by the gas and
internal energy increases
o If the arrow is reversed and the volume is decreasing (compression),
work is done on the gas and internal energy decreases
• A constant volume process is represented as a vertical line

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 o In a process with constant volume, the area under the curve is zero
o Therefore, no work is done when the volume stays the same

• Work is only done when the volume of a gas changes

Q. The volume occupied by 1.00 mol of a liquid at 50 oC is 2.4 × 10-5 m3. When
the liquid is vaporized at an atmospheric pressure of 1.03 × 105 Pa, the vapor
has a volume of 5.9 × 10-2 m3.The latent heat to vaporize 1.00 mol of this liquid
at 50 oC at atmospheric pressure is 3.48 × 104 J. Determine for this change of
state the increase in internal energy ΔU of the system.

• Step 1: Write down the first law of thermodynamics: ΔU = q + W

• Step 2: Write the value of heating q of the system

This is the latent heat, the heat required to vaporize the liquid = 3.48 × 104 J

• Step 3: Calculate the work done W = pΔV

• ΔV = final volume − initial volume = 5.9 × 10-2 − 2.4 × 10-5 = 0.058976 m3
• p = atmospheric pressure = 1.03 × 105 Pa
• W = (1.03 × 105) × 0.058976 = 6074.528 = 6.07 × 103 J
• Since the gas is expanding, this work done is negative
• W = −6.07 × 103 J
• Step 4: Substitute the values into first law of thermodynamics
• ΔU = 3.48 × 104 + (−6.07 × 103) = 28 730 = 29 000 J (2 s.f.)

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