Instruction Manual

and Experiment Guide

HEAT SYSTEM

4862.10

N.B.:

• Pictures, images and descriptions in this manual may not exactly correspond with
the actual items supplied.
• It is also important to note that the experiments in this manual are, only, suggestions.
They are not meant to indicate the limitation of the equipment, which can be used in
wide range of experiments, depending on the educational requirement of the teacher.
2
GENERAL DESCRIPTION:

This kit introduces basic concepts of thermology and heat experiments. It provides a framework for
understanding and quantitatively assessing introductory thermodynamics questions and problems. Some
experiments are devoted to examine more deeply various interesting thermodynamics aspects.

LIST OF EXPERIMENTS:

• Heat sensitivity
• Thermal equilibrium
• Expansion of liquids
• Measurement of the coefficient of volume expansion of water
• Fixed points of a thermometer
• Temperature measurement with an iron constantan thermocouple
• Linear expansion of solid
• Coefficient of expansion of iron and brass
• Bimetallic strip
• Example of use of a thermostat
• Evaporation
• Boiling and condensation
• Measurement of the boiling point of alcohol
• Boiling at below atmospheric pressure
• Boiling at above atmospheric pressure
• Measurement of the heat of evaporation of water
• The graph for the solidifying of paraffin
• Saturated and supersaturated solutions
• Wet – and dry- bulb hygrometer
• Expansion of air at constant pressure
• Expansion of air at constant volume
• Thermal convection in fluids
• Thermal conductivity of iron and brass
• Thermal conductivity of aluminium and copper
• Dependence of conductivity from dimensions of solid conductors
• Conduction of heat by water
• Absorption of thermal radiation
• Thermal insulation
• Construction of a simple Dewar vessel
• Heating different quantities of liquid
• Specific heat capacity of liquids
• Equilibrium temperature of mixed liquids
• Specific heat capacity of solid bodies
• Heat capacity of the calorimeter
• Conversion of mechanical energy into thermal energy
• Heat of solution
• Joule’s effect
• Expansion of ice
• Latent heat of fusion of ice
• Latent heat of vaporisation of water
• Evaporation of two different liquids
• Boiling point of a salt solution
• Boiling point elevation

3
 Index of related topics:
‘
‘Tea with milk’ problem ............................................................................................................... 25

A
Absorption of thermal radiation................................................................................................ 59

B
Boiling and condensation........................................................................................................... 58
Boiling at above the atmospheric pressure........................................................................... 70
Boiling at below the atmospheric pressure........................................................................... 69
Boiling point elevation................................................................................................................. 70
Boiling point of a salt solution .................................................................................................. 68

C
Comparison between calorimeters .......................................................................................... 23
Construction of a mixing calorimeter...................................................................................... 23
Construction of a simple Dewar vessel .................................................................................. 23
Conversion factor between joule and calories ..................................................................... 35
Cooling curve................................................................................................................................. 51

D
Dalton’s law of Partial Pressures.............................................................................................. 16

E
Equilibrium temperature of mixed liquids.............................................................................. 27
Evaporation of two different liquids ........................................................................................ 60
Expansion of ice............................................................................................................................ 38

F
Fixed points of a thermometer .................................................................................................. 15
Fourier equation ...................................................................................................................... 44, 53
Fourier law ........................................................................................................................................ 9
Functioning principle of a thermocouple ............................................................................... 64
Functioning principle of a thermostat..................................................................................... 67

H
Heat conduction ...................................................................................................................... 44, 53
Heat sensitivity ................................................................................................................................ 8
Heating different quantities of liquid ....................................................................................... 27

J
Joule experience ........................................................................................................................... 35

4
 L
Linear expansion of a solid ........................................................................................................ 48
Locke’s experience......................................................................................................................... 8

M
Measurement of the boiling point of alcohol......................................................................... 71
Measurement of the coefficient of volume expansion of water ....................................... 61
Mixing calorimeter ........................................................................................................................ 21
Moisture content ........................................................................................................................... 16

N
Newton’s law of heating or cooling............................................................................................ 9

P
Percentage saturation.................................................................................................................. 16
Phase transition ............................................................................................................................ 51
Psychrometer................................................................................................................................. 16
Pulse glass functioning principle............................................................................................. 58

R
Relative humidity .......................................................................................................................... 16

S
Saturated and supersaturated solution .................................................................................. 68
Seebeck coefficients .................................................................................................................... 65
Solution phenomena at different temperatures.................................................................... 56
Specific heat................................................................................................................................... 30
Specific heat of salt water .......................................................................................................... 35
Specific heat of water .................................................................................................................. 35
Specific latent heat of boiling of water.................................................................................... 41
Specific latent heat of fusion of ice.......................................................................................... 39

T
Thermal agitation .......................................................................................................................... 56
Thermal conduction coefficient ................................................................................................ 53
Thermal conductivity coefficient ................................................................................................ 9
Thermal contraction of air .......................................................................................................... 60
Thermal convection in fluids ..................................................................................................... 55
Thermal expansion of air ............................................................................................................ 60
Thermal expansion of water....................................................................................................... 61
Thermocouple calibration........................................................................................................... 65
Time constant ................................................................................................................................ 25
Time constant of a calorimeter............................................................................................ 21, 23
Time constant of a thermometer................................................................................................. 9

5
 W
Water equivalent of a calorimeter............................................................................................. 27
Water vapour .................................................................................................................................. 16
Wet and dry- bulb hygrometer................................................................................................... 16

6
POTASSIUM PERMANGANATE (CHEMICAL SAFETY DATA):
This kit contains potassium permanganate:

Common
Condy's crystals
synonyms

Formula KMnO4

Form: dark red to purple crystalline powder

Stability: Stable, but decomposes if heated above 150 C.
Physical Melting point: ca 150 C (decomposes)
properties Water solubility: moderate, produces solutions which are intensely coloured, even when
quite dilute
Specific gravity: 2.70

This material is harmful if swallowed or inhaled. It is also harmful if absorbed through the
Principal skin.
hazards Potassium permanganate is a strong oxidizing agent and may react very exothermically
with organic materials.

Wear safety glasses and keep the solid or solution from contact with the skin.. Take care
Safe handling
not to allow the solid to come into contact with flammable materials.

Eye contact: Immediately flush the eye with plenty of water. Continue for at least ten
minutes and call for medical help.
Emergency Skin contact: Wash off with plenty of water. Remove any contaminated clothing. If the skin
appears damaged, call for medical aid.
If swallowed: Call for immediate medical help.

Small amounts of very dilute potassium permanganate solution can be flushed down a
sink with a large quantity of water, unless local rules prohibit this. More concentrated
Disposal
solutions and waste solid should be retained for disposal by those in charge of the
laboratory.

Safety glasses. Protective gloves should not normally be necessary. If they are to be
Protective
used, nitrile will provide some protection, but may degrade upon contact with solid or
equipment
solution, so should be checked regularly and replaced if damage is apparent.

7
 Experiment 1.
RELATED TOPICS:

• Heat sensitivity
• Locke’s experience

The purpose of the experiment is to introduce the concept of temperature as felt by the human being.

ITEMS NEEDED:

• 3 beakers with cold, warm and hot water.

THEORY:

Perhaps the most famous discussion in modern Western philosophy of the experience of temperature, and
its underlying physiological concomitants, is given by Locke (1690/1959) in discussing secondary qualities in
the perception of physical objects:

We may be able to give an account how the same water, at the same time, may produce the idea of cold by
one hand and of heat by the other: whereas it is impossible that the same water, if those ideas were really in
it, should at the same time be both hot and cold. For, if we imagine warmth, as it is in our hands, to be
nothing but a certain sort and degree of motion in the minute particles of our nerves or animal spirits, we may
understand how it is possible that the same water may, at the same time, produce the sensations of heat in
one hand and cold in the other; which yet figure never does, that never producing the idea of a square by
one hand which has produced the idea of a globe by another. But if the sensation of heat and cold be
nothing but the increase or diminution of the motion of the minute parts of our bodies, caused by the
corpuscles of any other body, it is easy to be understood, that if that motion be greater in one hand than in
the other; if a body be applied to the two hands, which has in its minute particles a greater motion than in
those of one of the hands, and a less than in those of the other, it will increase the motion of the one hand
and lessen it in the other; and so cause the different sensations of heat and cold that depend thereon.

Science has found that thermal sensitivity is mediated by a number of different neuronal receptors. These
receptors are dorsal root ganglion neurons with cell bodies located near the spinal cord.
Among these receptors are those dedicated to sensing temperatures less than a person’s adapted skin
temperature (termed "cold" receptors), temperatures greater than a person’s adapted skin temperature
(termed "warm" receptors), receptors that serve to sense significant heat in association with pain (a type of
nociceptor), and receptors that serve to sense significant cold in association with pain (also a type of
nociceptor). The peripheral terminal of all of these neurons is a bare nerve ending. Cold receptors are
activated in a range from about 1°C to 20°C below normal skin temperature, approximately 34°C.
Warm receptors are activated in the range of about 32°C to 45°C. Above about 45°C, the discharge of warm
receptors decreases, and the nociceptors associated with the sensation of heat and pain respond.

Hence heat sensitivity is related to the initial temperature of our hands and we need a more objective method
to measure what is called “heat”.

PROCEDURE:

• Prepare three beaker. One with cold water (e.g. with melting ice), another with warm water at room
thermal equilibrium and the last one with hot water (after having placed the beaker on the burner for
a while)
• Dip two fingers into the beakers with cold and hot water and wait some minutes
• Dip both the previous fingers in the beaker with warm water.
• Analyse the differences produced in different sensations

8
 Experiment 2.
RELATED TOPICS:

• Time constant of a thermometer

• Fourier law
• Newton’s law of heating or cooling
• Thermal conductivity coefficient

The purpose of the experiment is to give a quantitative explanation of the thermometer’s time constant. This
is important since it gives insight on the heat sensitivity of our thermometer.

ITEMS NEEDED:

• Mercury thermometer
• Beaker
• Calorimeter
• Stop-watch

THEORY:

Let us suppose we have a thermometer at room thermal equilibrium with temperature equal to T0. If we place
at t=0 seconds the thermometer in the beaker with boiling water at T1 = 100 °C it’s possible to observe the
following behaviour on the thermometer reading as a function of time:

9
The ideal thermometer’s behaviour would be

This difference can be explained in the following manner. Let us suppose the environment is not influenced
by the thermometer.
When we place the thermometer in the beaker at temperature T1 the following sequence of snapshots is
what happens to the system composed by the environment (boiling water), the glass of the thermometer and
the mercury inside the glass:

10
Once the steady state situation of snapshot (d is established, the heat quantity dQ that is transmitted in the
time dt from the environment at temperature T1 to the mercury at T2=T(t) is (by the Fourier law, see details
calculations):
dQ kA kA
= [T1 − T2 ] = [T1 − T (t ) ] (1)
dt l l
where k is a constant that depends from the material (glass in this case) that build the thermometer.
It follows a rising of the mercury’s temperature
dQ = CdT (t ) (2)
where C is the heat capacity of the mercury.
By equating (1) with (2) we have
kA
[T1 − T (t )] dt = CdT (t ) (3)
l
from which
dT (t ) kA
= dt (4)
T1 − T (t ) lC
lC
a differential equation with separate variables. By direct integration and by posing τ= we get
kA
t
− dT (t )
t
1 [T1 − T (t )] t
∫0 T1 − T (t ) ∫0 − τ dt ⇒ ln [T1 − T (0)] = − τ
= (5)

or
t
−
T (t ) = T1 + [T (0) − T1 ] ⋅ e τ
(6)
which is exactly the observed behaviour of the real thermometer (an exponential trend to the final
temperature T1). Equation (6) is also called Newton’s law of heating or cooling.

11
From equation (6) it’s clear that to reach the temperature T1- hT1 (0<h<1) with a thermometer starting at
T(0)<T1 we have to wait a time
⎡ T (0) ⎤
t * = τ ⎢ln(1 − ) − ln(h) ⎥ (7)
⎣ T1 ⎦
For example with h=1/100 and τ=3.8 s, T1=100 °C, T(0)=20°C we have the following graph for equation (7)
time
17.5
15
12.5
10
7.5

H
L
5
2.5
T 0 T1
0.2 0.4 0.6 0.8 1
This means that if we want the thermometer reaches a temperature between 99°C and 100°C we have to
wait a time at least of 17 seconds.
⎡ T (0) ⎤
The maximum time limit we have to wait is given by lim τ ⎢ln(1 − ) − ln(h) ⎥ or
⎣ T1 ⎦
T (0)
→0
T1

1
tmax = τ ln( ) (8)
h
after this time we are sure that the temperature will lie between T1- hT1 and T1.

The time constant τ has time dimensions and represents the time is needed in order to reduce the
temperature difference T1 – T0 at 1/e of the initial value. The smaller is τ the more “quick” or “ready” can be
said the thermometer.

PROCEDURE:

Put the water at T1 in the calorimeter. This one is needed since we want to limit at maximum the heat
exchange with the surroundings. Now sink the thermometer (that was a room temperature T0) into the
calorimeter and observe the behaviour of the mercury when it’s raising.

EXPERIMENTAL DATA:

The same arguments exposed above hold for whatever temperature measuring system.
Here are some experimental data for a thermocouple connected to a datalogger.

12
From the fit it’s clear how in this case the time constant τ , in this case, is roughly 3.8 seconds.

DETAILS CALCULATION:

The Fourier law for the heat conduction (concerning only the stationary processes and not the transients)
can be stated by observing the following picture of an infinitesimal piece of a plate of length l and area A with
the two faces placed at different temperatures T1 and T2:

During the time dt the heat flow through the infinitesimal volume is experimentally given by
dQ dT
= −kdS (9)
dt dx
cal
where k is the thermal conductivity coefficient of the material (measured in ).
m ⋅ sec⋅°C
This is called the Fourier law. Otherwise said the heat loss per unit time and unit area is proportional to the
temperature gradient.
If we need a law for the heat conduction over an homogeneous tile with parallel plates of area S and
thickness l with S>>l we can apply the Fourier law as follows.

13
 dQ
Since we are considering steady state, this means that is not depending on x, so by integration over the
dt
entire length l and the entire area S of the plates we have
l T
2 T 2 l
dQ dQ
∫0 dt ∫ T∫ ∫ dT dx = − kA [T2 − T1 ]
dt ∫0
dx = − k dS dT = − kA ⇒ (10)
area 1 T1

or
dQ kA kA
= − [T2 − T1 ] = [T1 − T2 ] (11)
dt l l
which is exactly the equation we used.

14
 Experiment 3.
RELATED TOPICS:

• Fixed points of a thermometer

The purpose of the experiment is to verify the calibration of a mercury thermometer.

ITEMS NEEDED:

• Mercury thermometer
• Beaker
• Filtering flask with side tube

THEORY:

The fixed point of a thermometer are determined with the melting ice (0 °C) and the boiling water (100 °C)
both at 1 atm = 760 Hg mm.

PROCEDURE:

• Prepare some crunched ice in the beaker and wait until the ice is melted (a stirrer can be useful).
After that it’s possible to introduce the mercury thermometer into the beaker and take a reading of
the temperature’s error with respect to 0 °C. Remember that only the coexistence of both the solid
phase (ice) and liquid phase (melted ice) at 1 atm is a guarantee that the temperature should be 0
°C.
• After that prepare the same thermometer aw indicated in the above picture. It’s important that the
thermometer’s bulb remains placed under the side tube of the filtering flask. Wait the water’s boiling
and take a reading of the temperature’s error with respect to 100 °C. Remember that only the
coexistence of both the liquid phase (water) and gas phase (water vapour) at 1 atm is a guarantee
that the temperature should be 100 °C.

15
 Experiment 4.
RELATED TOPICS:

• Wet and dry- bulb hygrometer

• Psychrometer
• Dalton’s law of Partial Pressures
• Water vapour
• Moisture content
• Percentage saturation
• Relative humidity

The purpose of the experiment is to introduce the basics concepts of psychrometry.

ITEMS NEEDED:

• 2 mercury thermometers
• (cotton)
• (rubber band)

THEORY AND PROCEDURE:

The evaporation phenomenon requires heat to take place. By placing two mercury thermometers one of
which with the base into a piece of wet cotton it’s possible to observe the temperature difference between
them. Anyway the theory details are more subtle.
Psychrometry is the study of atmospheric air and its associated water vapour. Air comprises a mixture of
gases of which nitrogen makes up 78%, oxygen 21% and carbon dioxide and the inert gases (such as argon,
neon, krypton, helium etc.) the remainder.
These are known as the dry gases of the atmosphere.
In the air mixture, the dry gases and associated water vapour behave according to ‘Dalton’s law of Partial
Pressures’. That is they behave independently of one another and the pressure each exerts combine to
produce an overall ‘atmospheric pressure’.
Since at normal temperatures and pressures we are unable to condense these gases out from the
atmosphere, for the purpose of psychrometry, this mixture of gases can be treated as if it were a single
‘ideal’ or perfect gas behaving as a single element known as ‘dry air’.

16
In addition to these dry gases, the air also contains varying amounts of water vapour. At normal
temperatures and pressures, water is able to exist in both a liquid and a gaseous (or vapour) form, but it
cannot be treated in the same way as the other gases of the atmosphere because its quantity, and hence
proportion are continually varying.
Water vapour is said to be associated with dry air and the more vapour associated with the dry gases, the
more humid the air. At sea level, atmospheric pressure is normally within the range 95 to 105 Pa, but this
depends upon weather conditions.
The agreed international standard atmosphere has a pressure of 101.325 kPa (1013.25 mbar) and this
reduces at the rate 0.013 kPa per metre of height above sea level and increases at the same rate below sea
level.
The water vapour is completely independent of the dry atmospheric gases, and its behaviour is not affected
by their presence of absence, but for any given temperature there is a maximum amount of vapour that can
be absorbed or associated with a given volume of air. In addition, although the actual quantity of water is
quite small, it can have a dramatic effect on our perception of comfort.
(Under certain conditions the mass of water vapour will change due to condensation or evaporation (known
as dehumidification and humidification respectively), but the mass of dry air will remain constant. It is
therefore convenient to relate all properties of the mixture to the mass of dry air rather than to the combined
mass of air and water vapour).
Heat is a form of internal energy. This is a thermodynamic property and represents the internal energy of the
molecules. With increase temperature there is an increase in molecular activity and thus more water can
escape from the liquid into the gas as water vapour or steam. After a while however, even at this increased
temperature, the air will become fully saturated with water vapour so that no more water can evaporate
unless we again increase the temperature. The pressure produced by the water vapour in this fully
saturated condition is known as the saturated vapour pressure (pss) and since at a given temperature the air
cannot absorb more water than its saturated condition, the saturated vapour pressure is the maximum
pressure of water vapour that can occur at any given temperature.
Eventually of course, if we continue to supply heat the water will boil, and this will occur when the saturated
vapour pressure is equal to the atmospheric pressure.
Normal air temperature, as you might expect, can be measured by a normal mercury-in-glass thermometer
This is known as the Dry-bulb temperature (tdb) because the bulb of the thermometer is kept dry (as opposed
to the wet-bulb thermometer which we will introduce later). Vapour pressure (ps) is the actual pressure of
vapour existing at any particular location and time and temperature and is a property of the moisture content
of the air.
Dry-bulb temperature and vapour pressure are the two basic parameters which determine the humid
condition of atmospheric air, but other properties can be derived from them and likewise, they can be derived
from other properties. In practice we are not really interested in the pressure exerted by the vapour in a
mixture of air and water vapour, but we do need to know the quantity of water that exists at any time. One
way of measuring this amount in by the moisture content and can be expressed in kg of water vapour per kg
of dry air (kg/kg of dry air). [The term ‘humidity ratio’ was used in the past, but is not common today].
mass of water vapour ms
g= = (12)
mass of dry air ma
Percentage saturation is a useful guide to comfort as the human body tends to respond to relative saturation
rather than moisture content, and is the ratio between the actual moisture content of the sample (gs) and the
moisture content of a sample of saturated air (gss), at the same temperature.
moisture content of sample g
µ (%) = ×100 = s × 100 (13)
moisture content of saturated air g ss
Although percentage saturation is the preferred method of expressing the humidity ratio, relative humidity is
another method of measuring the amount of water vapour present in the air, and is a hangover from the days
of ‘imperial’ measurement. It is the ratio of the vapour pressure of an air sample to the saturated vapour
pressure at the same temperature, and is usually expressed as a percentage.
partial pressure of water vapour in sample p
rh(%) = × 100 = s ×100 (14)
partial pressure of water vapour in saturated air pss
at the same dry-bulb temperature.

17
Percentage saturation or relative humidity are frequently used in specifications as a requirement of air
humidity conditions. However, as the relationship between vapour pressure and moisture content is not quite
linear, their will always be a slight (but not usually significant) difference between them.
We are now in a position to derive useful expressions for moisture content and percentage saturation in
terms of partial pressure and hence compare percentage saturation with relative humidity.
If we consider the humid air mixture, the moisture (vapour) content of the air can be expressed either as a
specific value or as a ratio, as we noted before, of the mass of vapour to the mass of dry air.
Thus by definition
ms ns ⋅ ( molecular weight ) s
g= = (15)
ma na ⋅ ( molecular weight )a
pV
where n is the number of moles. But from the perfect gas law we have n= and so
RT
psVs R Ta ( molecular weight ) s ps Vs Ta 18.016 ps
g= = = 0.622 (16)
R Ts paVa ( molecular weight )a Ts pa Va 28.97 pa

where we have assumed the Vs=Va and Ts=Ta.

We also know from Dalton’s law of partial pressure that pa = patm − ps , therefore
ps
g = 0.622 (17)
patm − ps
The psychrometric equation links the dry-bulb and the wet-bulb temperatures to their corresponding vapour
pressures and to the atmospheric pressure.
Consider air flowing across the bulb of a wet-bulb thermometer:

Moisture will be evaporated from the muslin cloth sleeve around the bulb and will be taken up (associated)
with the surrounding air. For this evaporation to take place heat must be supplied and this can only come
from the surrounding air, i.e the latent heat of evaporation gained by the moisture on the surface of the

18
muslin as it associates with the air, must equal the sensibile heat lost from the surrounding air, in other words
there must be a drop in the wet-bulb temperature to compensate for the increase in mosture content to the
air around it.
At the surface of the muslin sleeve the air is considered to be at saturation moisture content (gss’), so that
the latent heat gain is proportional to the difference in moisture content between the film of air surrounding
the muslin sleeve and the surrounding air, i.e. to ( gss’ – gs ).
Similary, the sensible heat lost is proportional to the temperature difference between the bulb and the
ambient temperature, i.e. to (T – T’), and since one process is the cause of the other we may equate them
as:
B ( g ss '− g s ) = C (T − T ') (18)
where B and C are constants which relate to surface area and latent heat. But from equation (17) for
moisture content, we known that:
ps ps
g s = 0.622 0.622
patm − ps patm
(19)
pss ' p '
g ss ' = 0.622 0.622 ss
patm − pss patm
since ps and pss’ are both very small compared to patm. Hence by substituting (19) in (18) we get
0.622
B ( pss '− ps ) = C (T − T ' ) (20)
patm
from which we obtain
Cpatm
ps = pss '− (T − T ') = pss '− A patm (T − T ') (21)
B 0.622
where A is known as the psychrometric constant (strictly speaking is not constant and is better to express it
as A = ( f + gT ') where f = 6.600x10-4 and g=7.750x10-7 and the difference between the dry-bulb and the
wet-bulb temperatures (T – T’) is known as the wet-bulb depression.
Now the rate of moisture evaporation is different if the air is above or below freezing point (0°C) and between
still and moving air (a standard speed of 2 m/s is used, but between about 2 m/s and 20 m/s the effect of air
velocity is practically constant).
When working with the psychrometric equation, it is important to remember that the saturated vapour
pressure (pss’) is taken at the wet-bulb temperature.
Since we want to calculate relative humidity we have to apply equation (14). By substituting into it equation
(21) we get
ps ⎡ A patm ⎤
rh(%) = × 100 = ⎢1 − (T − T ')⎥ ×100 (22)
pss ' ⎣ pss ' ⎦
Now we need to know pss’ as a function of temperature and other parameters (Magnus equation). It’s
possible to show that
2937.4
Log10 pss ' = −4.9283Log10T '− + 22.5518 (23)
T'

for T’>0°C. Finally, by substituting it into (22) we get

rh(%) =
⎧⎪ ⎡ −2937.4 ⎤ ⎫⎪
−⎨23.5518+ ⎢ ⎥⎬
⎢⎣ (T +273) ⎥⎦ ⎪⎭
⎪⎩
(T + 273) ×
4.9283
10 (24)

⎡ ⎧⎪⎨23.5518+⎡⎢ −2937.4 ⎤⎥⎫⎪⎬ ⎤

⎢10⎩⎪ ⎢⎣ (T '+273) ⎥⎦ ⎭⎪
( T '+ 273) − ( 6.600 ⋅10−4 + 7.570 ⋅10−7 ⋅ T ') ⋅ patm ⋅ (T − T ')⎥ ×100
−4.9283

⎢ ⎥
⎣ ⎦
in this formula we only have to measure T, T’ and patm to get rh.
For example if p=1 atm=760 mm Hg and T=21°C we have the following graph:

19
 rh %
100
H
L
80

60

40

20

T'
5 10 15 20
-20
If the wet bulb temperature is T’=17°C this means, by applying equation (24), that rh(%)≅70%.

20
 Experiment 5.
RELATED TOPICS:

• Mixing calorimeter
• Time constant of a calorimeter

The purpose of the experiment is to introduce the mixing calorimeter and to give an explanation of the
calorimeter’s time constant. This is important since it gives insight on “how good” is the calorimeter.

ITEMS NEEDED:

• Thermometer
• Heat source
• Beaker
• Calorimeter
• Stop-watch

THEORY:

The calorimeter is a physical system thermically isolated from the surroundings. By using it, it’s possible to
measure the heat quantity exchanged between the calorimeter and whatever other system that don’t interact
chemically with the calorimeter.
The “mixing calorimeter” is constituted by a thermos with a known mass of liquid (in general water) of known
specific heat.
Every calorimeter cannot be considered as a perfect adiabatic system (thermically isolated from outside).
There are unavoidably heat losses so it’s important to establish how much “adiabatic” is.
The law that is governing the heat exchange is (see preceding experiment)
dQ
= δ [T1 − T2 ] = δ [T1 − T (t ) ] (25)
dt
where T1 is the environment temperature and δ=kA/l is a constant that can be interpreted as “heat
conductivity” of the calorimeters walls.
It follows the following behaviour for the calorimeter’s temperature (see preceding experiment)
t
−
T (t ) = T1 + [T (0) − T1 ] ⋅ e τc
(26)
lC
with τc = where T(0) is the starting temperature of the calorimeter, and τc is the time constant of the
kA
calorimeter.

21
 t
If t<< τc we can approximate equation (26) with T (t ) T (0) + [T1 − T (0) ] . So, as a first approximation,
τc
we have a linear trend of T(t).

PROCEDURE:

Put the water at T1 in the calorimeter. Now sink the thermometer (that was a room temperature T0) into the
calorimeter and take the temperature every fixed amount of time.

EXPERIMENTAL DATA:

Here are some experimental data collected with a thermocouple connected to a datalogger. The first part of
the graph is like the preceding experiment. But now we are interested on how is decreasing the temperature
of the calorimeter.

From the exponential fit it’s easy to calculate the time constant of the calorimeter as τc = 750 seconds.

22
 Experiment 6.
RELATED TOPICS:

• Construction of a mixing calorimeter

• Time constant of a calorimeter
• Comparison between calorimeters
• Construction of a simple Dewar vessel

The purpose of the experiment is to show how are involved the various parts of a mixing calorimeter. By
repeating this experiment in various configurations it’s possible to investigate on the effect of the various
parts on the calorimeter’s adiabaticity.

ITEMS NEEDED:

Same of the preceding experiment.

PROCEDURE:

Repeat the same procedure of the preceding experiment by using only the internal vessel of the mixing
calorimeter. It’s possible also to repeat the experiment with other configurations (e.g. without cover or with
thermal insulate between the walls, etc.). This is a method for the construction of a simple Dewar vessel.

EXPERIMENTAL DATA:

Here are some experimental data collected with thermocouple connected to a datalogger. Note how the time
constant is considerably smaller if compared to the preceding experiment. That means we are working with a
worse calorimeter.

23
From the exponential fit it’s easy to calculate the time constant of the calorimeter as τc = 665 seconds. The
time constant gives us a quantitative way to compare various kind of calorimeters. Moreover it tell us which is
the time interval we must take in account to operate with the calorimeter.

24
 Experiment 7.
RELATED TOPICS:

• ‘Tea with milk’ problem

• Time constant

The purpose of the experiment is to resolve the following problem. At the bar of a railway station a traveller is
sitting on a table with a boiling tea cup and a small cup of cold milk. Since his train is living in few minutes,
which is the best action he can do to cool down his tea with the milk in a given amount of time?

ITEMS NEEDED:

• 2 Thermometer
• 2 big vessels
• 2 small vessels
• Balance
• Stop-watch

PROCEDURE:

You can simulate the tea with a given amount of water m1 (e.g. 120 g) at a temperature T1 bigger than the
room temperature T0. Analogously the milk can be simulated with m0 (e.g. 40 g) of water at room
temperature T0.
Put the same amount of water m1 at T1 in each one of the big vessels that are containing thermometers. For
1
a mercury thermometer after a time (see previous experiments) t ≥ τ ln( ) = 3.8 ⋅ ln(100) 17 sec we are
h
sure that the measured temperature are until T1- T1/100 and T1.

EXPERIMENTAL DATA:

25
The preceding figure shows experimental data collected with thermocouple connected to a datalogger. Note
how the time constant is bigger in Experiment A than in B. The experiment shows clearly the solution of the
problem.

26
 Experiment 8.
RELATED TOPICS:

• Water equivalent of a calorimeter

• Heating different quantities of liquid
• Equilibrium temperature of mixed liquids

The purpose of the experiment is to introduce the concept of water equivalent of a calorimeter.

ITEMS NEEDED:

• Calorimeter
• 2 thermometers
• stop-watch
• balance
• graduated vessels

THEORY:

Let us start from the heat definition

Q = C ⋅ ∆T = c M ⋅ ∆T (27)
cal cal
where C is the heat capacity (measured in ), c is the specific heat (measured in ) and ∆T is the
°C g ⋅°C
temperature difference.

The mixing calorimeter is composed by a known mass of water and various rigid parts.
For a known mass Mw of water the heat capacity is Cw = M w cw . For the solid parts of the calorimeter (inside
and outside vessels, cover, stirrer, etc.) the unknown heat capacity is Cc.
By introducing in the calorimeter a mass of water M1 at temperature T1 and subsequently a mass of water M2
at temperature T2< T1 we can use equation (27) to determine the sole unknown variable Cc.
In fact at the equilibrium we have
( M 1cw + Cc )∆T = M 2 cw ∆T ' ⇒ ( M 1cw + Cc )(T1 − Θ) = M 2 cw (Θ − T2 ) (28)
where Θ is the equilibrium temperature (obviously the same arguments holds if T2> T1).
It’s now possible to introduce the concept of “water equivalent” of the calorimeter by posing
Cc = M * cw (29)
and by substituting it in (28)we have

27
 M 2 (Θ − T2 ) − M 1 (T1 − Θ)
M* = (30)
T1 − Θ

PROCEDURE:

If the time constant of the calorimeter would be infinite, T1 (before the mixing process) and Θ (after the
mixing process) could be considered constant.
As we saw in previous experiments this is not the case and we have to consider the following experimental
situation before and after the mixing:

By interpolating at time = 227 seconds, it’s possible to recover T1= 75 °C.

28
From which it’s possible to recover T2= 49 °C
Note how the mixing operation affects the experimental results.
The best think to do is to interpolate data at the time during which the mixing is occurring.
For the displayed data we have M1= 150 g, M2 = 150 g, T1= 75 °C, T2= 20 °C and Θ = 49 °C and so by
applying equation (30) we get M* ≅ 20 g

29
 Experiment 9.
RELATED TOPICS:

• Specific heat

The purpose of the experiment is to show how it’s possible to obtain an experimental value of the specific
heat.

ITEMS NEEDED:

• Calorimeter
• 2 thermometers
• stop-watch
• balance
• graduated vessels
• solid block of various substances (copper, brass, iron, …)

THEORY:

The same argument of the preceding experiments.

Let us start from the heat definition
Q = C ⋅ ∆T = Mc ⋅ ∆T (31)
cal cal
where C is the heat capacity (measured in ), c is the specific heat (measured in ) and ∆T is the
°C g ⋅°C
temperature difference.
The mixing calorimeter is composed by a known mass of water and various rigid parts.
For a known mass Mw of water the heat capacity is Cw = M w cw . For the solid parts of the calorimeter (inside
and outside vessels, cover, stirrer, etc.) the unknown heat capacity is Cc=M*cw.
By introducing in the calorimeter a mass of water M1 at temperature T1 and subsequently a solid block of
mass M2 with unknown specific heat cx at temperature T2< T1 we can use equation (27).
In fact at the equilibrium we have
( M 1cw + Cc )∆T = M 2 cx ∆T ' ⇒ ( M 1cw + M * cw )(T1 − Θ) = M 2 cx (Θ − T2 ) (32)
where Θ is the equilibrium temperature (obviously the same arguments holds if T2> T1).
From (28)we have
( M 1 + M *)cw (T1 − Θ)
cx = (33)
M 2 (Θ − T2 )

30
PROCEDURE:

• Let us consider the copper block.

As we saw in the preceding experiment we have to consider the following experimental situation before and
after the mixing (M2=98 g, T2=22.3 °C, M1= 220 g, M*=20 g):

From which it’s possible to recover T1= 85 °C.

From which it’s possible to recover Θ = 83 °C.

31
And so, by applying equation (33)we have cx≅ 0.1 cal/g°C to be compared with the tabulated value for
copper of cx = 0.09 cal/g°C.

• Let us consider the brass block.

By interpolation it’s possible to recover T1= 80 °C.

From which it’s possible to recover Θ = 77 °C.

32
And so, by applying equation (33)with (M2=98 g, T2=20 °C, M1= 220 g, M*=20 g) we have again that cx≅
0.1 cal/g°C to be compared with the tabulated value for brass that is very similar to that of copper since
brass is essentially an alloy consisting mainly of copper (over 50%) and zinc

• Let us consider the iron block.

From which it’s possible to recover T1= 82 °C.

33
From which it’s possible to recover Θ = 78 °C.
And so, by applying equation (33)with (M2=101 g, T2=23 °C, M1= 220 g, M*=20 g) we have that cx≅ 0.17
cal/g°C to be compared with the tabulated value of iron of cx = 0.11 cal/g°C.

34
 Experiment 10.
RELATED TOPICS:

• Joule experience
• Specific heat of water
• Specific heat of salt water
• Conversion factor between joule and calories

The purpose of the experiment is to measure the specific heat of water and to get the conversion factor
between joule and calories.

ITEMS NEEDED:

• Calorimeter
• Joule’s law unit
• Power supply (not included in the kit)
• 1 thermometers
• stop-watch
• balance

THEORY:

During the heating process of water the heat quantity released by the Joule’s law unit in a time dt is
dQ = j ⋅ c ⋅ MdT (t ) + dQ '+ λ (T )dm (34)
cal
where c is the specific heat of water (measured in ), j is the conversion factor between Joule and
g ⋅°C
joule
calories (in this way j·c is expressed in ), M is the mass of water expressed in grams,
g ⋅°C
j ⋅ c ⋅ MdT (t ) the heat quantity adsorbed by the system expressed in joule, dQ’ is the heat loss towards the
surroundings expressed in joule, and λ (T ) dm is the heat necessary to evaporate a mass of water dm.
The power dissipated by the Joule’s law unit is W=V⋅I, so the heat quantity dQ released to the system is
dQ = Wdt expressed in joule.
If it’s possible to neglect λ (T )dm compared to j ⋅ cMdT (t ) and dQ’ we have
dQ = j ⋅ c ⋅ MdT (t ) + dQ '+ λ (T )dm ⇒ Wdt = j ⋅ c ⋅ MdT (t ) + dQ ' (35)

35
but by the Fourier law (since we are supposing the heat loss mainly by conduction) expressed in joule we
kA
have dQ ' = j ⋅ [T (t ) − TA ] dt = δ [T (t ) − TA ] dt where TA is the initial temperature and δ is expressed in
l
joule
. By substituting it into (35)we have
°C ⋅ sec
dt dT (t )
= (36)
j ⋅ cM W − δ [T (t ) − TA ]
j ⋅c⋅M
By integrating with T(t=0)=TA and by posing τ= (expressed in seconds), we have
δ
−δ dT (t ) ⎛ δ ⎞
t t
⇒ − = ln (W − δ [T (t ) − TA ]) = ln ⎜ 1 − [T (t ) − TA ] ⎟
dt t t
∫−
0
τ
=∫
0
W − δ [T (t ) − TA ] τ 0
⎝ W ⎠
(37)

or
W⎛ − ⎞
t
T (t ) = TA + ⎜1 − e ⎟
τ
δ ⎝
(38)
⎠
The time constant τ is independent from W but the limit value of temperature not, since we have
W
lim T (t ) = TA + (39)
t →∞ δ
PROCEDURE:

Here are some experimental data for W=24 Watt and M=345 g (we should consider also the equivalent in
water of the calorimeter but here we suppose it’s negligible).

W Wτ
From the fit we have that TA=19.5 °C, = 100°C and τ≅6100 sec. So we have
δ j ⋅c⋅M
Wτ W 6100 joule
j ⋅c = 4.2
M ⋅100 M ⋅100 g °C

36
 joule
which is the specific heat of water expressed in . Since, by definition, the specific heat of water is also
g °C
cal
given by 1 (in the temperature range 14.5-15.5 °C) we have
g °C
joule
j 4.2 (40)
cal
to be compared with the tabulated value of j=4.1868 joule/cal.

Repeat the experience by using salt water (with a given concentration of salt) and see if the specific heat is
lower, higher or remains the same.

37
 Experiment 11.
RELATED TOPICS:

• Expansion of ice

The purpose of the experiment is to determine what happens when the ice melts

ITEMS NEEDED:

• Graduated cylinder
• Beaker
• (ice)
• (stirrer)

THEORY AND PROCEDURE:

During the melting of the ice the water volume changes.

• Fill the graduated cylinder exactly to a fixed mark (e.g. 50 ml) with water and record the volume V1.
• Put some ice cubes in the graduated cylinder and with the help of a stirrer hold them just below the
water’s surface. Read immediately the new volume V2.
• Heat the graduated cylinder (e.g. with hands) until the melting is complete and record the new
volume V3.
• The volume of the ice cubes is V2- V1, the volume change is V2- V3
• Calculate the volume change with respect to the volume of the initial cubes (literature’s value is 11%)

The change in water’s density between 0° and 20°C is negligible.

38
 Experiment 12.
RELATED TOPICS:

• Specific latent heat of fusion of ice

The purpose of the experiment is to measure the latent heat of fusion of ice.

ITEMS NEEDED:

• Calorimeter
• 1 thermometers
• stop-watch
• ice blocks
• balance

THEORY:

If you have a glass of a cool drink, well supplied with ice, you can expect its temperature to drop until it is
close to 0 ºC. You also can expect (and can easily check with a thermometer) that it will remain cold,
regardless of the outside temperature, as long as there remains some unmelted ice in the drink. Only after all
the ice has melted will the temperature of the drink begin to rise. Why is this?
When a solid substance changes from the solid phase to the liquid phase, energy must be supplied in order
to overcome the molecular attractions between the constituent particles of the solid. This energy must be
supplied externally, normally as heat, and does not bring about a change in temperature. We call this energy
latent heat (the word "latent" means "invisible"). The latent heat is the energy released or absorbed during a
change of state. With this in mind, we define the specific latent heat of fusion:

"The specific latent heat of fusion of a substance is the amount of heat required to convert unit mass of the
solid into the liquid without a change in temperature."

To measure the specific latent heat of fusion of ice it’s possible to use a calorimeter with a mass Mw of water
at a temperature Tw > 0°C.
The heat quantity Q released by the water initially present and by the calorimeter is the sum of the heat
quantity Q1 one needs to melt the ice and the heat quantity Q2 one needs to bring the mass of water of the
melted ice from the fusion temperature to the equilibrium temperature Θ.
If M* is the water equivalent of the calorimeter we have:
Q = cw ( M w + M *) (Tw − Θ ) (41)
and if Mi is the melting ice mass and λ is the specific latent heat of fusion we have
Q1 = M i λ (42)

39
and
Q2 = cw M i ( Θ − Ti ) (43)
where Ti is the temperature of the melting ice. So we have
Q = Q1 + Q2 ⇒ cw ( M w + M *) (Tw − Θ ) = M i λ + cw M i ( Θ − Ti ) (44)
or
cw ( M w + M *) (Tw − Θ ) − cw M i ( Θ − Ti )
λ= (45)
Mi
cal
measured in .
g

PROCEDURE:

Pay attention to have Ti=0°C since when the ice is just extracted from a freezer it can be at a temperature
considerably lower of 0°C. This can be achieved by putting the ice in a beaker with water, shaking it for a
while and then by removing the water. When the ice begins itself to melt and to produce water by using a
thermometer it’s possible to check if it’s at 0°C.
Mi can be determined, once the melting has take place, by difference with respect to the initial water’s
weight. Θ can be determined by taking the minimum value of the temperature before it starts to increase.
The followings are experimental data for Mw=130 g, Tw=20°C, M*=20g, Mi=20g.

By applying equation (45) we get λ ≅ 70 cal/g to be compared with the tabulated value of 80 cal/g.

40
 Experiment 13.
RELATED TOPICS:

• Specific latent heat of vaporization of water

The purpose of the experiment is to measure the specific latent heat of vaporization of water.

ITEMS NEEDED:

• Calorimeter
• Joule’s law unit
• Power supply (not included in the kit)
• Graduated cylinder
• 1 thermometers
• Stop-watch
• Balance

THEORY:

A change of state from liquid to vapour at constant temperature also requires the input of energy, called the
latent heat of vaporization. This implies that while a liquid undergoes a change to the vapour state at the
normal boiling point, the temperature of the liquid will not rise beyond the temperature of the boiling point.
The latent heat of evaporation is the energy required to overcome the molecular forces of attraction between
the particles of a liquid, and bring them to the vapour state, where such attractions are minimal.
The definition of the specific latent heat of vaporization is

'The specific latent heat of vaporization is the amount of heat required to convert unit mass of a liquid into the
vapour without a change in temperature’

For water at its normal boiling point of 100 ºC, the latent specific latent heat of vaporization is 2260 kJ⋅kg-1 or
2260 J⋅g-1.This means that to convert 1 kg of water at 100 ºC to 1 kg of steam at 100 ºC, 2260 kJ of heat
must be absorbed by the water. Conversely, when 1 kg of steam at 100 ºC condenses to give 1 kg of water
at 100 ºC, 2260 kJ of heat will be released to the surroundings.
Latent heats of vaporization vary widely, and values should always be accompanied by the temperatures at
which they were measured (these are not necessarily the normal boiling points).

Let us suppose we heat a known mass of water until it boils, then wait a little continuing to heat the water
and finally let the water cooling.
• During the heating phase the temperature is governed by (see previous experiments)

41
 W⎛ − ⎞
t
T (t ) = TA + ⎜1 − e ⎟
τ
δ ⎝ ⎠
(46)

j ⋅c⋅ M
where τ= .
δ
• During the boiling phase we have (see preceding experiments)
dQ = j ⋅ c ⋅ MdT (t ) + dQ '+ λ (T )dm = δ [TB − TA ] dt + λB dm (47)
because when the water is boiling the system (calorimeter + water) is no more adsorbing heat
( j ⋅ c ⋅ MdT (t ) ) and all the heat is needed for the phase transition ( λ (T ) → λB ) and losses

[
outwards ( δ TB − TA ) ]
But dQ = Wdt and so, by integrating equation (47), we have
W⎡ δ ⎤
λB = ⎢1 − (TB − TA ) ⎥ ( t2 − t1 ) (48)
m⎣ W ⎦
where m is the mass of water that evaporates in the time interval t2-t1 during the boiling phase. If
now, during the boiling phase, we interrupt at time t*>t2 the heat source, the water stops boiling.
• During the cooling phase we have
0 = j ⋅ c ⋅ MdT (t ) + δ [T (t ) − TA ] dt + λ (T )dm (49)
if it’s possible to neglect λ (T ) dm compared to j ⋅ cMdT (t ) and dQ’. By separating the variables
and integrating we have
t −t *
−
T (t ) = (TB − TA ) ⋅ e τ
+ TA (50)
j ⋅c⋅ M
where τ= is the same as before.
δ
We derived this equation since equation (46) is not good for temperatures near the boiling point. This is due
to the fact that water is a bad heat conductor and it starts to boil near the resistances of the Joule’s law unit.
This is why we need another equation to determine τ.
So, by using equations (46)and (50)we can determine δ and τ and then by using equation (48)it’s
possible to obtain λB.

PROCEDURE:

To determine W it’s a simple matter of recording the value of the tension V and current I applied to the joule’s
law unit and multiply them.
To determine δ and τ we can use equation equations (46)and (50).

42
In the preceding graph we have m ≅ 10 g, t2-t1 ≅ 300 sec, TB ≅ 100 °C, TA ≅ 43 °C, τ ≅ 2235 sec W ≅ 40 W
and W/δ ≅ -20 and so we get λB ≅ 2300 joule/g to be compared with the tabulated value of 2260 J/g.

43
 Experiment 14.
RELATED TOPICS:

• Heat conduction
• Fourier equation

The purpose of the experiment is to show qualitatively the heat conduction in a rod

ITEMS NEEDED:

• Beaker with boiling water

• 1 thermometers
• 1 u-shaped rod with thermal insulation jacket
• stop-watch

THEORY:

The situation described in a previous experiment was a steady-state situation, in which the temperature was
a function of x but not of time. We are now going to consider a more general situation in which the
temperature may vary in time as well as in space.

44
In this case the temperature gradient is written as a partial derivative, and is not uniform down the length of
∂T ∂T ∂ 2T
the rod. We'll suppose it is at x and + dx at x +dx.
∂x ∂x ∂x 2
Consider the heat flow into and out of the portion between x and x +dx. The rate of flow into this portion at x
∂T ⎛ ∂T ∂ 2T ⎞
is by the Fourier law − kdS and the rate of flow out at x+dx is − kdS ⎜ + 2 dx ⎟ so that the net flow
∂x ⎝ ∂x ∂x ⎠
∂T
2
∂T ∂T
of heat into that portion is kdS dx . This must be equal to cM = c ρ dSdx where ρ is the density
∂x 2
∂t ∂t
and c is the specific heat.
Therefore
∂ 2T ∂T
k 2 = cρ (51)
∂x ∂t
This can be written as
∂T ∂ 2T
=D 2 (52)
∂t ∂x
k
where D = is the thermal diffusivity measured in m2/s. Equation (52) is the Fourier (heat conduction)
cρ
equation.
The Fourier equation, differently from the Fourier law which is valid only for steady states, allows us to study
the transient thermal phenomena
From the form of this equation, it is obvious (once it has been pointed out!) that a solution could be found in
which T(x, t) is solely a function of x2/t, or, for that matter, x/t1/2.
Thus, let
x
u= (53)
t
by substitution into (52)we get a second order total differential equation
d 2T 1 dT
D 2
=− u (54)
du 2 du

45
 dT
by posing T ' = we get an even easier first order differential equation
du
dT ' 1
D = − uT ' (55)
du 2
Upon integration we obtain
1 2
ln(T ') = − u +A (56)
4D
or
1 2
− u
T ' = A⋅e 4D
(57)
We have to integrate again, with respect to u
1 2
− u
T = ∫ A⋅e 4D
du (58)
By using the two temperature T1 and T2 it’s possible to determine A in the following manner.
Now, T = T1 at x = 0 for any t > 0. That is, T = T1 for u = 0. And T = T2 at t = 0 for any x > 0. That is, T = T2
for u = ∞. Therefore
0
−
1 2
u π T2 − T1
T1 − T2 = A ⋅ ∫ e 4D
du = −2 A D ⇒ A= (59)
∞
2 πD
By integrating equation (58)for an undetermined T(x,t) we have
T2 − T1 1 2 0
− u
T1 − T ( x, t ) = ⋅ ∫ e 4 D du (60)
πD x
t
or
⎛ x ⎞
T ( x, t ) = T1 − (T1 − T2 ) erf ⎜ ⎟ (61)
⎝ 2 Dt ⎠
r
2
∫ e dy (it’s easy to show that erf(0)=0 and
− y2
where we have introduced the error function erf ( r ) =
π 0
erf(∞)=1)
If we take a graph of equation (61) we get

Temperature
60

55

50

45

40

35

30

25

time
1000 2000 3000 4000 5000 6000

PROCEDURE:

Place the rod with thermal insulation jacket as indicated in the picture above.

46
By using a thermometer and a stop-watch it’s possible to collect the following data quite similar to the
preceding graph. Keep in mind that our mathematical model is far quite different from reality and the
experience is to be intended qualitatively:

47
 Experiment 15.
RELATED TOPICS:

• Linear expansion of a solid

The purpose of the experiment is to show qualitatively and quantitatively the linear expansion of a solid
substance.

ITEMS NEEDED:

• Beaker
• Cylinder of different solid substances
• 1 thermometer
• stick meter (not included in the kit)
• comparator 1/100 mm
• stop-watch

THEORY:

From a macroscopic point of view the linear expansion of a solid can be explained as follows. Let us take in
consideration a solid cylinder and fix our attention on its length l.
If we vary the temperature and this fact is not responsible of any solid’s state change or chemical alteration
we have from the experiments that
l = l0 (1 + α (T ) ∆T ) (62)
where α(T) is the coefficient of linear expansion of the solid substance.
In practical applications α(T) is usually considered as a constant α by choosing its mean value in the range
of temperatures of interest.
In this case equation (62) becomes
l = l0 (1 + α ∆T ) (63)
or
l − l0 ∆l
α= = (64)
l0 ∆T l0 ∆T

48
Now let us consider our cylinder immersed in a beaker full of water at temperature T0

If we replace the water at temperature T0 with water at temperature T > T0 the different expansion of glass
and solid cylinder can be imagined as

So, by writing equation (63)both for glass (with linear expansion coefficient β) and solid cylinder (with linear
expansion coefficient α), we have
l ' = l '0 (1 + β ∆T )
(65)
l = l0 (1 + α ∆T )
Adding both sides
⎛ l '0 β ⎞
( l '+ l ) = ( l '0 + l0 ) + l0α ∆T ⎜⎜1 + ⎟
⎟
( l '0 + l0 ) + l0α ∆T (66)
⎝ l0α ⎠
l '0 β
where we have neglected since l’0 << l0 and β < α (or at maximum of the same order of magnitude).
l0α
Finally equation (66) can be written as

49
 ∆L
α= (67)
l0 ∆T
where ∆L = ( l '+ l ) − ( l '0 + l0 ) is the total variation in length of the system composed by the beaker and the
cylinder.

PROCEDURE:

With the calliper take a measure of the cylinder’s length l0 at temperature T0

Place the cylinder into the beaker under the comparator. Pour the water at T > T0 into the beaker until the
cylinder is completely sink. Wait a little in order to give to the cylinder the time needed to reach thermal
equilibrium with water.
Now start the measurements and observe how many centesimal parts of a millimeter is the contraction ∆L
observed on the comparator, during a jump ∆T in the temperature.
For example, with an aluminium cylinder of length l0 = 121 mm with a ∆T≅16 °C we have a ∆L≅0.06 mm and
by applying equation (67) we recover α ≅ 30⋅10-6 °C to be compared with the tabulated value of α ≅ 23⋅10-6
°C

50
 Experiment 16.
RELATED TOPICS:

• Phase transition
• Cooling curve

The purpose of the experiment is to show qualitatively the phase transition and the cooling curve of the
paraffin.

ITEMS NEEDED:

• Beaker
• Test tube
• Paraffin
• 1 thermometer
• stop-watch

THEORY:

One of the simplest forms of thermal analysis is to measure the temperature of a heated sample of
predetermined composition as a function of time as the sample is allowed to cool. As we shall see,
discontinuities in the slope of the cooling curve indicate various types of phase transformations that may be
occurring as a function of temperature. This technique can also be used as the sample is being heated.
Consider for example an unary system of water. Assume that the liquid water has been heated to a
temperature near, but still below, the boiling point and then allowed to air cool to room temperature. A plot of
the water temperature as a function of time would resemble the cooling curve in (a). The temperature
decreases monotonically as a function of time with no discontinuities in the slope of the curve. The rate at
which the temperature decreases depends upon the rate at which heat is extracted from the system.

Now place the liquid water in a freezer and continue to cool the system. As the freezing temperature is
reached, ice will begin to form at the expense of the water. The freezing process evolves heat, which is
released back into the system, and the system is able to maintain a constant temperature.
The cooling curve experiences a thermal arrest as the water reaches its freezing temperature; the
temperature of the system does not change with time, even though heat is being continually withdrawn from
the system. The temperature is maintained at the freezing temperature through the latent heat of fusion
released by the solidifying water. After the water is completely frozen, a cooling curve similar to the
preceding is again observed (b). Thus the thermal arrest serves to identify the freezing temperature of the
water in this unary system. The thermal arrest is indicative of isothermal freezing, or some other type of
isothermal transformation.

51
THEORY:

The paraffin is used instead of water because of its easy of use (temperature of fusion in an easy range).
Pour a sufficient amount of water in the beaker and the test tube with the paraffin inside and a thermometer.
Then bring the water to the boiling point and observe how the paraffin inside the test tube is melted.
Take away the test tube from the beaker with boiling water and start the measurement of temperature as a
function of time.
The cooling curve is like the following:

From the graph its clear how the phase transition occurs at T≅58°C

52
 Experiment 17.
RELATED TOPICS:

• Heat conduction
• Fourier equation
• Thermal conduction coefficient

The purpose of the experiment is to show quantitatively the heat conduction in a rod and to measure the
thermal conduction coefficient

ITEMS NEEDED:

• Beaker with boiling water

• 1 thermometers
• various u-shaped rods with thermal insulation jacket
• stop-watch

THEORY:

The situation described in a previous experiment was a transient situation, in which the temperature was a
function of time in a prefixed point of the rod. If we set in a steady-state situation we have to apply the
Fourier law
dQ kA
= − ∆T (68)
dt l
to the rod of section area A and length l (the length must be that not immersed in water) and diameter 2R
Let us suppose one end of the rod at constant temperature (e.g. boiling water temperature) and the other
end in a small becker containing m grams of water at room temperature (∆T=100°C-room temperature). If
the water temperature in the becker is increased by ∆T’=T(t)-Tinitial we have

53
 dQ d ∆T ' dT (t )
= cw m = cw m (69)
dt dt dt
By equating equation (68) and equation (69)we get k:
cw ml dT (t ) ml dT (t ) ml dT (t ) cal
k= = = in (70)
A∆T dt A∆T dt π R 2 ∆T dt °C ⋅ m ⋅ sec
PROCEDURE:

Place one end of the rod with insulation jacket in the becker with boiling water. The other end must be placed
in the small becker with a known quantity of water.
Take a temperature reading after some minutes in order to avoid transient states.
Here are some experimental data were the initial part has been ignored (transient states). The slope has
been calculated for the steepest part of the curve.

dT (t ) °C
In our case m = 50 g, l = 0.300 m, A = π⋅R2=π⋅ (0.010)2m2, ∆T=(100-21)°C and = 0.001038 . By
dt sec
cal
applying equation (70)we have k = 2.5 corresponding to a stainless steel of type AISI 30.
m°C sec
Repeat the experiment with various rods of different diameter and material.

54
 Experiment 18.
RELATED TOPICS:

• Thermal convection in fluids

The purpose of the experiment is to show qualitatively the convection heat transfer.

ITEMS NEEDED:

• Beaker
• Water or better distilled water (not included in the kit)
• Potassium permanganate

THEORY:

One type of heat transfer is convection. The heat transfer studied in this experiment is the forced convection,
which happens due to density differences.
The water in the beaker will be heated in the base, being the highest temperature in the centre of the base.
That implies that the molecules, closer to the centre of the base, have larger temperature than the molecules
that are placed above them. That is, in the vertical axis of the beaker it exists a temperature gradient,
reducing the temperature as it is arriving to the top water surface. It is noted that the gradient is not linear
because close to the beaker walls we have water with smaller temperature than in the centre. This is the key
for the forced convection phenomenon.
We can follow the path of a molecule located in the centre of the base, in the initial instant. When heating the
molecule, its density will become less, implicating that it will move up. When moving up its temperature will
decrease. The molecule moves up until it reaches the minimum temperature point. The minimum
temperature point is close to the top and to the beaker walls. Of course the molecule is not going to the limit
of the surface, because before arriving to that point its temperature will becomes lower enough in a way that
it will become denser, and move immediately down.
In the displacement to the hot base surface, the molecule will prefer the zone close to the walls because it
offers a range of temperatures more favourable. Another reason, for the existence of a certain molecule
path, is because in the central zone is where most of the hot molecules move upward, offering an extra
resistance to the molecule that is moving down

PROCEDURE:

Pour distilled water in a beaker, filling 3/4 of its total volume. Add some sodium permanganate crystals to
the water. The water shouldn't become total colored. The permanganate crystals should be deposited in the
bottom. (the permanganate should not be touched or ate because it is toxic. Use gloves and glasses!).
Place the beaker and heat it up. (while the heating is being done you will begin to notice a migration of water
from the base to top. That phenomenon is called convection heat transfer)

55
 Experiment 19.
RELATED TOPICS:

• Solution phenomena at different temperatures

• Thermal agitation

The purpose of the experiment is to show qualitatively the phenomenon of the thermal agitation.

ITEMS NEEDED:

• 2 beakers
• 2 thermometers
• 2 spoons (not included in the kit)
• water
• Potassium permanganate
• 1 spatula

THEORY:

In hot water all the processes are quicker since at higher temperatures the water has got more thermal
agitation.

PROCEDURE:

With the spatula prepare some crystals of potassium permanganate (the humidity can reduce them to small
blocks instead of separate cristals).
Just few crystals of potassium permanganate are necessary to follow the path in water and to show the
differences between hot and cold water. The crystals path is not linear both in hot and in cold water:

But in hot water the path is more different from the vertical:

56
At a certain point the diffusion process begins from bottom:

In hot water the solute diffuse more quickly:

This is due to the thermal agitation of hot water. In cold water are still evident the tracks of the crystals
transported by the micro air bubbles.

57
 Experiment 20.
RELATED TOPICS:

• Pulse glass functioning principle

• Boiling and condensation

The purpose of the experiment is to show how a pulse glass works.

ITEMS NEEDED:

• 1 pulse glass

THEORY:

This invention is due to Benjamin Franklin.

This simple device consists of a narrow tube bent at right angles at either end, with two larger spheres on the
ends. The tube is roughly one-third to one-half filled with water or alcohol, evacuated, and sealed. Because
of the vacuum, the liquid in the glass can be brought to a boil by holding it in one’s hand. Several toys are
now made from pulse glasses, including the ‘fever meter’ and the ‘drinking duck’.
In holding a pulse glass in your hand you can observe some surprising phenomena and experience some
curious sensations. As Franklin notes, “the instant it begins to boil a sudden coldness is felt in the ball held.”
What Franklin discovered was that the boiling temperature of water depends on the atmospheric pressure.
This observation influenced and inspired James Watt to generate power with a steam machine. The pulse
glass produced new knowledge and lead to many technological innovations and inventions. It gave the
scientist and inventor the confidence of being able to produce desired phenomena intentionally and control
some physical parameters purposively. The knowledge of these phenomena and their relations enables
know how. The observation of phenomena is thus fundamental both for science and technology.

PROCEDURE:

58
Hold the pulse glass so that the bulbs point up, and enclose one bulb with your hand to warm it. The heat
from your hand will change some of the liquid on that end to vapour, increasing the pressure in that end and
forcing the liquid into the other end.

59
 Experiment 21.
RELATED TOPICS:

• Absorption of thermal radiation

The purpose of the experiment is to show qualitatively the absorption of thermal radiation.

ITEMS NEEDED:

• 1 pulse glass

THEORY:

By using the same principle of the preceding experiment, if we cover one bulb of the pulse glass

and we expose it to the light sun it’s possible to watch the same effect of the preceding experiment.
This is due to the thermal radiation that is acting on the vapour tension and denotes the absorption of
thermal energy.

60
 Experiment 22.
RELATED TOPICS:

• Thermal expansion of air

• Thermal contraction of air
• Evaporation of two different liquids

The purpose of the experiment is to show qualitatively how the air is expanded when heated and contracted
when cooled.

ITEMS NEEDED:

• 1 filtering flask
• 1 mercury thermometer
• permanganate of potassium
• Drying tube, U-shaped used as a U-tube manometer
• rubber tube

THEORY:

The gases expand themselves (as liquids and metals) when heated and contract themselves when cooled.

PROCEDURE:

Once filled the u-tube manometer with a prefixed quantity of coloured water (with potassium permanganate)
connect the rubber tube to the filtering flask as indicated in the above picture.
Note the temperature and the start to heat the flask (by hand or using an heat source).
After a while it’s possible to observe how the air is expanded by measuring the level difference with the u-
tube manometer.
By letting cool the filtering flask it’s possible to observe the contraction of air.
To improve the effect it’s possible to insert some alcohol inside the filtering flask. Any way, now the pressure
increase is not only due to air but also to alcohol’s vapour tension.
This effect is due to the different evaporation behaviour of two different liquids.

61
 Experiment 23.
RELATED TOPICS:

• Thermal expansion of water

• Measurement of the coefficient of volume expansion of water

The purpose of the experiment is to show qualitatively how the water is expanded when heated.

ITEMS NEEDED:

• 1 filtering flask
• 1 graduated cylinder
• 1 mercury thermometer
• permanganate of potassium
• glass tube
• rubber tube

THEORY:

The liquids expand themselves (as gases and metals) when heated and contract themselves when cooled.
Anyway the liquid expansion, in the case of water, is not linear (the maximum density is reached at 4°C).
By neglecting this fact we can measure the magnitude’s order of the expansion coefficient α by applying the
supposed linear relation between volume’s variation and temperature difference:
V = V0 (1 + α ∆T ) (71)
or
∆V = α V0 ∆T (72)
PROCEDURE:

As shown in the above picture, fill the filtering flask connected to the tube with a measured quantity of
coloured water (with potassium permanganate) at room temperature with the graduated cylinder and record
its value V0.
Insert the rubber stop so that no water overflows. Make sure that no air bubbles are trapped under the
rubber stop.

62
Record the room temperature T0 and the start to heat the flask (by using the burner).
After a while it’s possible to observe how the water is expanded by measuring the level difference with the
tube ∆l.

By measuring the increase in volume

2
⎛d ⎞
∆V = π R ∆l = π ⎜ ⎟ ∆l
2
(73)
⎝2⎠
where d is the tube’s diameter, by applying equation (72), it’s possible to recover α.
Some experimental data are V0= 1l, T0=19°C, ∆T=16°C, ∆V=5.39 x 10-6 m3 from which α≅0.0003 °C-1

63
 Experiment 24.
RELATED TOPICS:

• Functioning principle of a thermocouple

The purpose of the experiment is to show the functioning principle of a thermocouple.

ITEMS NEEDED:

• 1 thermocouple type T (copper-constantan)

• 1 digital multimeter

THEORY:

A thermocouple is a device primarily used for the measurement of temperature.

It is based upon the findings of Seebeck (1821) who showed that a small electric current will flow in a circuit
composed of two dissimilar conductors when their junctions are kept at different temperatures. The
electromotive force (e.m.f.) produced under these conditions is known as the Seebeck effect. The pair of
conductors that constitute the thermoelectric circuit is called thermocouple
The reverse is also true (Peltier effect) and if one furnishes a tension to a thermocouple, a temperature
difference between the two junctions is established.

PROCEDURE:

Connect the thermocouple’s terminals to the digital multimeter and observe how the potential difference is
increased by heating the thermocouple head (for example with a lighter).

64
 Experiment 25.
RELATED TOPICS:

• Seebeck coefficients
• Thermocouple calibration

The purpose of the experiment is to show how to use and calibrate a thermocouple.

ITEMS NEEDED:

• 1 thermocouple type T (copper-constantan)

• 1 digital multimeter
• 1 beaker
• 2 mercury thermometers

THEORY:

Imagine a conductor with an applied temperature gradient. Electrons (or holes) will thermally diffuse from the
hot end to the cold end, and carry their charge with them. This charge builds up on the cold end and creates
an electric field inside the sample. When the current generated by this electric field cancels the flow due to
thermal diffusion, equilibrium is reached. The Seebeck coefficient (also called the thermopower) is the ratio
between the electric field and the temperature gradient (or equivalently, the ratio between the voltage
difference and temperature difference between the ends of the sample). So, roughly speaking, the Seebeck
coefficient can be thought of as a measure of the coupling between the thermal and electrical currents in a
material. Note that the sign of the Seebeck coefficient depends on the sign of the charge carriers (whether
positive or negative charge builds up on the cold end). So measuring the Seebeck coefficient is a way to
determine whether the charge carriers in a particular material are holes or electrons.
Let us consider the following figure:

The potential difference between A and B can be written as

∆V = VA − VB = (VA − VC ) + (VC − VB ) (74)

65
 r uur b
Since the potential difference between two points a and b is defined as the line integral ∆V =
r r
a
E ⋅ dl
uuur
∫
where E is the electric field, and by the definition of the Seebeck coefficients, we have that E = S (T )∇T it
results from equation (74) that

C dT B dT
∆V = ∫ SCopper (T ) dx + ∫ SCons tan tan (T ) dx
A dx C dx
or
TC TB =TA =TAB
∆V = ∫ SCopper (T ) dT + ∫ SCons tan tan (T ) dT =
TA =TB =TAB TC
TC
= ∫ ⎡⎣ SCopper (T ) − SCons tan tan (T ) ⎤⎦ dT
TAB
If A and B are at the same reference temperature and if the Seebeck coefficients are nearly constant across
the targeted temperature range (in other words SCopper (T ) → SCopper and SCons tan tan (T ) → SCons tan tan ) , the
integral in the above equation can be simplified, allowing one to solve directly for the temperature at the point
C
∆V = ( SCopper − SCons tan tan )(TC − TAB ) = ( SCopper − SCons tan tan )∆T
In conclusion:
∆V ∆V
∆T = = (75)
( SCopper − SCons tan tan ) ∆S
or
∆V
TC = TAB + (76)
∆S
DETAILS:

In practice the Seebeck coefficient are not independent from temperature and so thermocouple vendors will
provide calibration functions for their products. These functions are usually high order polynomials and are
calibrated with respect to a certain reference temperature, e.g., 0°C. Suppose that the coefficients of the
calibration polynomials are a0, a1, a2, ..., an. The temperature at the probe can then be related to the voltage
output as
TC = a0 + a1∆V + a2 ( ∆V ) + ... + an ( ∆V )
2 n
(77)
Note that the above formula is effective only if the reference temperature TAB=a0 in the experiment is kept the
same as the reference temperature specified on the data sheet. Furthermore, these coefficients are unit
sensitive. Make sure to use the vendor-specified temperature unit when plugging in numbers..

PROCEDURE:

Heat some water in a beaker with a mercury thermometer inside.

Take a measure of the room temperature TAB with another mercury thermometer.
Put the head of the thermocouple connected to the digital multimeter inside the beaker and observe how
many millivolts ∆V correspond to the water temperature TC.
By applying equation (76) it’s possible to deduce ∆S for copper and constantan by keeping in mind the
approximations we made about the reference temperature.
Example of experimental data are ∆V=3.2 mV, TAB=23°C, TC=98°C, from which ∆S=0.04 mV/°C quite in
accordance with tabulated values.
After that, by knowing ∆S, it’s possible to use the thermocouple as a thermometer.

66
 Experiment 26.
RELATED TOPICS:

• Functioning principle of a thermostat

The purpose of the experiment is to show the functioning principle of a thermostat.

ITEMS NEEDED:

• 1 bimetallic strip
• 1 digital multimeter

THEORY AND PROCEDURE:

By using a lighter it’s possible to heat the bimetallic strip.

Most metals (and many other materials) expand when heated. But each metal expands at a different rate.
The bimetal strip is made up of two metals that have very different expansion rates.
The metal on the outside expands more quickly than the metal on the inside. This causes the strip to curl up
when it is heated. The heat energy is converted into mechanical energy as the strip curls up.
To make more clear the phenomenon it’s possible to use the digital multimeter with the resistance buzzer.

67
 Experiment 27.
RELATED TOPICS:

• Saturated and supersaturated solution

• Boiling point of a salt solution

The purpose of the experiment is to introduce the concepts of saturated and supersaturated solution .

ITEMS NEEDED:

• 1 mercury thermometer
• 1 beaker
• 1 test tube
• (salt)

THEORY AND PROCEDURE:

• Bring 150 cc of water to boil into the beaker

• With the mercury thermometer read the boil temperature and pour inside the beaker a spoon of salt
• It’s possible to observe that the salt dissolves itself, while the boil temperature decreases.
• Continue to dissolve salt into water until it’s impossible to dissolve it any more and measure the boil
temperature
• Turn off the burner and pour a small quantity of water (not the undissolved remaining salt!) into the
test tube. Let cool the test tube and observe how the salt is again formed into its crystalline form. If
it’s not the case, after 10 minutes, add a single salt crystal to trigger this phenomenon.

CONCLUSIONS:

The salt coefficient of solubility depends on the temperature of the solvent. If a solution is saturated at 90-
100 °C, by cooling it we get a supersaturated solution and part of the solute lay down in crystals form.

68
 Experiment 28.
RELATED TOPICS:

• Boiling at below the atmospheric pressure

The purpose of the experiment is to show qualitatively how the water can regain boiling at a temperature
below 100°C when the pressure is below the atmospheric pressure .

ITEMS NEEDED:

• 1 mercury thermometer
• 1 filtering flask

THEORY AND PROCEDURE:

• Bring 150 cc of water to boil into the filtering flask. Wait 5 minutes after the boiling point is reached.
In the meanwhile prepare the rubber stop with the thermometer as in the following drawing

• Close the filtering flask with the rubber stop and thermometer. Same think for the lateral tube with
only a rubber stop. By using the clamp, incline the filtering flask in order to wet the bulb of the
thermometer

• Wash the filtering flask with cool water and observe how it starts again to boil

CONCLUSIONS:

During the boiling, the vapours throws away the air above the water. After having closed the flask and
washed it with cool water, the internal vapours condense themselves reducing the pressure.
The vapour bubbles can reach the environment temperature at a pressure lower than the atmospheric
pressure

69
 Experiment 29.
RELATED TOPICS:

• Boiling at above the atmospheric pressure

• Boiling point elevation

The purpose of the experiment is to show qualitatively how the water can boil at a temperature above 100°C
when the pressure is above the atmospheric pressure .

ITEMS NEEDED:

• 1 mercury thermometer
• 1 filtering flask
• a piece of rubber tube
• 1 graduated cylinder
• 1 glass tube
• (mercury)

THEORY AND PROCEDURE:

Prepare the apparatus as shown in the preceding drawing.

• Bring 100 cc of water to boil into the filtering flask and cap it with the rubber stop and thermometer.
Pour some mercury into the graduated cylinder roughly until half its height.
• When the water boils dip the glass tube into the graduated cylinder and observe how the boiling
temperature is varying. When the vapour is crossing into the mercury, turn of the burner. Now the
pressure inside the filtering flask is greater than the atmospheric pressure of a value equals to the
mercury millimetres in the graduated cylinder (1 atm= 760 mm Hg)

CONCLUSIONS:

When the pressure is above 1 atm the boiling temperature of water is greater then 100°C and the increase of
the temperature is proportional to the increase in pressure.

70
 Experiment 30.
RELATED TOPICS:

• Measurement of the boiling point of alcohol

The purpose of the experiment is to measure the boiling point of alcohol .

ITEMS NEEDED:

• 2 mercury thermometer
• 1 beaker
• 1 test tube
• (alcohol)

THEORY AND PROCEDURE:

Prepare the apparatus as shown in the preceding drawing.

• Bring 200 cc of water to boil into the beaker and pour some alcohol (nearly 10 cc) inside the test
tube that must be dipped into the beaker. Both the test tube and the beaker have a mercury
thermometer placed inside.
• When the alcohol boils record the temperature with the termometer inside the test tube and turn off
the burner

CONCLUSIONS:

The alcohol boils at 78°C.

71
 APPENDIX
Basics of experimental error theory

We can say that everything we known about the physical world has an inherent
uncertainty. In particular, when we experimentally investigate something there is always an
“experimental error” and an “experimental precision”. Since one of the main features of
experiments is their reproducibility, it is very important to deal with this subject in order to
be able to explain how good our results are. This is possible with “experimental error
theory”, a scientific approach to this problem.

Let us consider the following example: find the density of a solid rubber cube.

o First trial (with very raw instrument). We can estimate that the mass of the
cube is nearly 50 g and the length of a side is nearly 6 cm. So the density
would be:
M M
ρ= = 3 = 0,23148... . There are many questions: “Where can I stop with
V L
decimal digits to communicate my result?” “Is it better to have precision on
the mass measurement or on length measurement?” “How do we combine
our experimental error on the mass measurement with the experimental error
on length measurement?”
o Second trial (with more accurate instruments). By using an electronic
balance and a meter stick I find a mass of 60g and a side length of 5,4 cm.
So the density would be:
M M
ρ= = 3 = 0,381039475... . We still need to answer the questions posed
V L
above but we also have to answer a new question: “What makes this trial
better than the first one?”
o Third trial (with much more accurate instruments to measure the side
length). If we improve the accuracy of the length measurement, for example
by using a vernier caliper, the problem becomes more involved. This is due
to the fact that we do not get the same result if we make more than one
measurement. Instead we have a set of different measurements like (5,455
cm; 5,425 cm; 5,465 cm; …). So we are again faced with the question:
“Which one of the measurements (5,455 cm; 5,425 cm; 5,465 cm; …) do
should I take?”

Therefore, the more we analyse the problem the more it gets involved. To search for a
possible solution we can start from the third trial and observe that, generally speaking,
when we improve the accuracy of an instrument we reach a point at which the
experimental results are not unique but are scattered around some value as illustrated in
this graph:

72
If the number of measurements N is greater then about 30, the distribution of the
experimental data is bell-shaped and has a value X for which there is a maximum and
around which the data are scattered in a nearly symmetrical way. It is also possible to
distinguish a value that determines an interval around X into which a significant
percentage of the measurements are placed. We need to answer the questions: “Is X the
best estimate of our measurement?”, “How much can we rely on this value?” and “What
percentage of the measurements are in the interval X-σ and X+σ ?”

To express these questions mathematically, we could try a prototype function that fits our
data and that expresses the probability to get a particular measurement value:
1

0.8

0.6

0.4

0.2

-3 -2 -1 1 2 3
this is the graphical representation of the function
f ( x) = e − x
2

If we want to centre the function around the value X we use the expression x-X in place of
x, and if we want to control the scattering of the measurements around X it’s possible to
divide (x-X)2 by 2σ2.
The following figure shows f(x) with X=2 and σ=1;1.5;2

73
 1 1 1

0.8 0.8 0.8

0.6 0.6 0.6

0.4 0.4 0.4

0.2 0.2 0.2

-2 2 4 6 8 10 -2 2 4 6 8 10 -2 2 4 6 8 10

Finally, if we want to control the area under the curve we have to multiply it by a
normalization factor Aσ that would depend on σ .
Therefore our prototype function is:
( x − X )2
−
f ( x ) = Aσ ⋅ e 2⋅σ 2
(78)
where X is the value for which we have the maximum and σ determines how the
measurements are scattered around X. This is called a “Gaussian function” or a “Normal
function”, but the underlying data represent a distribution (still called Gaussian) and not a
function. It can be proved that the Gaussian distribution is derivable from the binomial
distribution assuming that the number of measurements N Æ ∞ and σ remains constant.

The physical meaning of all this is that we do not describe a measurement with a single
number but rather with a set of values each one with its own probability to appear as an
experimental datum. This probability is governed by the “Gaussian distribution”. There is
an analogy with quantum mechanics (for example with the wave packet of a particle)
where the interpretation is that if we make a measure of the position of the particle then
the probability to obtain a particular value is governed by the Gaussian function and is
never a well defined fixed value.

Let us determine the value of Aσ in (78). We must have a probability of 1 to get a

measurement in the range from -∞ to +∞ (that is, if we perform a measurement we are
certain to get some kind of result no matter how large or how small that result is):
+∞ 1
∫−∞ f ( x)dx = 1 ⇒ Aσ = 2π ⋅σ
To give an interpretation of σ we can ask what happens if we are only interested in the
probability of finding measurements in the range from X-σ to X+σ instead of the range
from -∞ to +∞:
2
t
X +σ 1 +1 −
∫ X −σ
f ( x) dx = ⋅ ∫ e 2 dt
2π −1
0.68

so σ, also called then “standard deviation” (σ2 is called “variance”), is the amount of
uncertainty we have to allow for, in the most probable value X, if we want to claim a
roughly 68% chance of correctly predicting the result of any single measurement.

To determine X, also called the “mean value”, we consider a set of N measurements x1,
x2, …, xN. The probability to get a single result between xi and xi+dx is:

74
 ( x − xi )2
1 −
Pi = ⋅e 2⋅σ 2

σ 2π
so the probability to get all the results (viewed as independent events) is:
N
∑ ( x − xi )
2

1 − i=1
P = P1 × P2 × ... × PN α ⋅e 2⋅σ 2
σ N

Since we are speaking about the probability P to get all the results and we can suppose to
have already done our experiment with a set of real results what should be the value of P?

If we accept the maximum likelihood principle we can make an analogy with entropy and
say that P is proportional to the entropy obtained from our experiment. The value X must
be a point of maximum entropy. By the second principle of thermodynamics we have to
maximize P, otherwise said X is the value of x that minimize the exponent:
d ⎡N 2⎤
⎢ ∑
dx ⎣ i =1
( x − xi ) ⎥ = 0 from which it results:
⎦
1 N
X=∑ xi
N i =1
(79)

that is, the mean value X is the arithmetic mean and describes all the collected data since
it is the value for which the maximum entropy is obtained for our set of data.

⎡ ∑ ( x − xi ) ⎤
N
2

d ⎢ 1 − i=1 2⋅σ 2 ⎥
To determine σ we can proceed in the same way ⎢ ⋅e ⎥ = 0 from which:
dσ ⎢ σ N ⎥
⎢⎣ ⎥⎦
1 N
σ= ∑ ( x − xi )
2
(80)
N i =1
But what should be use instead of x in equation (80)? If we use (79) then equation (80) is
2
1 N ⎛1 ⎞
slightly self-referential because σ = ∑ ⎜ ( x1 + ... + xi + ... + xN ) − xi ⎟ and the i-esim term
N i =1 ⎝ N ⎠
appears two times. It is possible to show that the correct value of the standard deviation is:

1 N
σ= ∑ ( X − xi )
2
(81)
N − 1 i =1
Clearly σ is not defined for N=1 (we are assuming N greater of nearly 30, otherwise there
are better distributions to consider).

Suppose now we have a function Q of several variables Q = f ( a, b, c,...) and we want to

know how the experimental error on each variable contributes to Q.
We can say that by varying the variables, the quantity Q varies of:

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 ∂Q ∂Q ∂Q
∆a +∆Q =∆b + ∆c + ...
∂a ∂b ∂c
and if we identify our uncertainty ∆x with the standard deviation σx we can say that:
∂Q ∂Q ∂Q
σQ = σa + σb + σ c + ... (82)
∂a ∂b ∂c
the modulus is due to the fact that errors could cancel each other and we want to consider
the maximum error.
We could do better, obtaining a smaller value, if the variables are normal and independent,
1 N
by starting from (81) σ Q = ∑ ( − Qi ) where Qi = f (ai , bi , ci ,...) is the i-esim value of
2

N − 1 i =1
Q by taking the i-esim value of each variable of our set of data, = f ( A, B, C ,...) is the
mean value of Q by taking the mean value of each variable of our set of data.
2 2 2
⎛ ∂Q ∂Q ⎞ ⎛ ∂Q ⎞ ⎛ ∂Q ⎞
( − Qi ) = ( ∆Qi ) = ⎜ ∆ai + ∆bi + ... ⎟ ⎟ ( ∆ai ) + ⎜ ⎟ ( ∆bi ) + ...
2 2 2 2
Since ⎜ (by
⎝ ∂ai ∂bi ⎠ ⎝ ∂ai ⎠ ⎝ ∂bi ⎠
neglecting terms of higher order) we have:

⎛ ∂Q ⎞ 1 N ∂Q
2 2

( ∆ai ) + ⎜⎛ ⎟⎞
1 N
σQ = ⎜ ∑ ∑ ( ∆bi ) + ...
2 2
⎟
⎝ ∂a ⎠ 14
N − 14i244
=1
3 ⎝ ∂b ⎠ 14 N − 14i244
=1
3
σ a2 σ b2

or
⎛ ∂Q ⎞ ⎛ ∂Q ⎞
2 2

σQ = ⎜ ⎟ σa + ⎜
2
⎟ σ b + ...
2
(83)
⎝ ∂a ⎠ ⎝ ∂b ⎠
which is better of (82) since it’s always lower.
N
1
Suppose now that the function Q is just the arithmetic mean X =
N
∑x .
i =1
i By applying

equation (83) we get

2 2
⎛ ∂X ⎞ 2 ⎛ ∂X ⎞ 2
σX = ⎜ ⎟ σ x1 + ⎜ ⎟ σ x2 + ... (84)
⎝ ∂x1 ⎠ ⎝ ∂x2 ⎠
∂X ∂ ⎛1 N
⎞ 1
but =
∂xi ∂xi ⎜⎝ N
∑ x ⎟⎠ = N and σ
i =1
i x1 = σ x2 = ... = σ and so

σ
σX = (85)
N
which is called “standard deviation of the mean”. Analogously to the “standard deviation”, it
tells us how good is the mean value X and we can assume it as the amount of uncertainty
we have to allow for if we want to claim a roughly 68% chance of correctly predicting the
result of any other mean value it is possible to obtain.
σQ
It is also useful to speak about relative error instead of absolute error σ Q . The relative
Q
error can be expressed in percentage.

For example let us return to the problem of determine the density of a cube.

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Now, the function Q is the density which is function of the mass M and the side length L:
M
ρ = 3 . If M = 60 g and L = 54mm it’s easy to find that the mean value is
L
60 g g
ρ = 3 3 = 3,81 ⋅10−4 3
54 cm cm
By applying equation (82) we have that the relative error is:
σ ρ 1 ∂ρ 1 ∂ρ L3 1 L3 −3M 1 3
= σM + σL = σM + σL = σM + σL .
ρ ρ ∂M ρ ∂L M L 3
M L 4
M L
If we can suppose the precision of the mass measurement is σ M = 2 g and the precision of
the length measurement is σ L = 1mm we have:
σ ρ 2 3 ⋅1
= + 3,3% + 5, 6% = 8,9%
ρ 60 54
(this says it is more important to make a careful length measurement than a careful mass
measurement).
By applying equation (83) we get a better (lower) estimate of the density error:
σρ σ M 2 9 ⋅σ L2 22 9 ⋅12
= + = + = 6,5% .
ρ M2 L2 60 2 542
This means that if we take another measurement of density there’s a probability of nearly
g
68% that the new value will lie between (3,8 ± 0, 2) ⋅10−4 3 .
cm
It is important to note that since the standard deviation on density is 0,2 x 10-4 g/cm3 we
can stop at the first decimal digit 3,8 x 10-4.

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