Chemistry - A.A. 2021-2022

Chemistry – A.A.
2021-2022
CHEMISTRY
Emma Angelini
Dipartimento di Scienza Applicata e Tecnologia - Politecnico di Torino
e-mail : emma.angelini@polito.it
E. Angelini – DISAT – Politecnico di Torino -1-

Chemistry – A.A. 2021-2022
LESSON 5
States of aggregation and changes of state
The fundamental states of nature that we take into consideration are: solid, liquid and gaseous. They
differ from each other in the characteristics indicated in the table.
Solids Liquids Gas

Own Shape Yes No No
Own Volume Yes Yes No
From this it can be seen that solids have their own shape and volume, fluids take on the shape of the
container that contains them. In particular, gases tend to fill all the space available to them .
The properties of matter in its three states of aggregation are essentially determined by the type and
extent of the interaction forces between the particles. The solid state is characterized by an ordered
distribution of the particles, the interparticle forces being very strong so that the particles have only
the possibility of oscillating around well-defined positions. This oscillation can be enhanced by the
action of the temperature. T
Solids have their own shape and volume and are considered incompressible. In the liquid state, the
intermolecular forces are strong enough but not to the point of preventing the movement of
particles.

Liquids are therefore easily deformable but also incompressible since their volume can only be
minimally varied with pressure and temperature.
Gaseous state: the intermolecular forces are practically negligible and the particles are arranged in
a completely disordered way. Gases therefore have neither volume nor shape of their own. Liquids
and gases are called fluids due to their ability to vary their shape.
Plasma: There is a fourth state of aggregation, plasma, which is obtained by bringing a gas to
temperatures above 5000 ° C. In this situation, one or more external electrons are detached giving
rise to the formation of ions; the plasma is therefore formed by cations and electrons in equilibrium
with each other. The stars are, for example, in the plasma state as is the matter present in the "neon
tubes". Any chemical element can exist in a gaseous, liquid and solid state. The transition from one
of these states to another is called a change of state.
Most of the elements, in environmental conditions, are in the solid state. The exceptions are
mercury and bromine which are in the liquid state and neon, helium, argon, krypton, xenon, radon,
hydrogen, nitrogen, oxygen, fluorine, chlorine which are in the gaseous state.
By varying the temperature or the pressure (or both), each element can change its ground state. By
increasing the temperature and decreasing the pressure, a gaseous solid-liquid passage is usually
obtained. Obviously, the reverse path is obtained by decreasing the temperature and increasing the
pressure.

Gas model:
A gas can be conceived according to the following model:
• Made up of very small corpuscles or particles, detached from each other and dispersed in space.
• Particles are endowed with movement without any relationship of mutual dependence; they
frequently collide with each other and with the walls of the container.
• The forces between the particles are very low.
• The actual volume of the particles is negligible compared to that of the container that holds the
gas.
Liquid model:
Liquids, intermediate between gases and solids, can be represented according to this model:
• Made up of very small corpuscles or particles very close to each other but which do not occupy
fixed positions; between one particle and another there are small gaps.
• Between the particles there are medium intensity attractive forces which, while forcing them to
remain in contact, allow them to slide over each other.
Solid model:
A solid can be represented by the following model:
• Made up of very small corpuscles or particles that are very close to each other.
• Among the particles there are very intense attractive forces which, in addition to keeping them
in close contact with each other, prevent any appreciable movement; however, it is admitted
that they can vibrate around their equilibrium positions while occupying an almost fixed
position.
• The particles can be distributed in space with regularity (ordered solids or crystalline) or
without any rules (disordered or amorphous solids).

International system of measurement
The following table represents the possible multiples and submultiples used in the metric
system. The relative symbols can be applied to all units of measurement of the International
System.
Prefix Symbol Value with
Tera T 1012
Giga G 109
Mega M 1000000 = 106
kilo k 1000 = 103
etto h 100 = 102
deca da 10
none Fundamental unit 1
deci d 0.1 = 10-1
centi c 0.01 = 10-2
milli m 0.001 = 10-3
micro µ 0.000001 = 10-6
nano n 10-9
pico p 10-12

Length
The basic unit in the International System is the meter (m), defined as Length.
The basic unit in the International System is the meter (m), defined as the length, at 0 ° C, of
a standard platinum-iridium ruler which is kept in Paris in the International Office of Weights
and Measures. Nowadays, for reasons of safety and precision, it is preferred to use as a
sample the wavelength, in vacuum, of a particular orange radiation emitted by the isotope
with mass number 86 of the krypton gas (1 m = 1650763.73 wavelengths) .
Volume:
Misura di una porzione finita di spazio
1 m3 = 1000 liters, 1 dm3 = 1 liter, 1 cm3 (c.c.) = 1 ml (milliliter), 1 mm3 = 1 µl (micro litr)
Pressure:
Force acting on the surface unit
Acceleration due to Earth's gravity = 9.8 m/s2
1 Newton = 1 kg m/s2
1 Pascal = 1 N/m2,
1 atmoshere = 760 mmHg (o torr) = 1.01325 x 105 Pascal = 101.325 kPa
The unit of pressure in the International System is Pascal, defined as the pressure exerted by
the force of one Newton on the surface of 1 m2. Since F = ma = 1Kg * 9.81 m / sec2 = 9.81
N, this means that a weight force of 9.81 Newton acts on the mass of one kilogram on the
earth. The obvious proportion dictates that if 9.81 N equals the weight force of 1000 grams, 1
N equals the weight force of 102 grams. In practice, the unit of measurement used for
chemical and chemical-physical systems is the atmosphere, derived from the measurements
of Evangelista Torricelli (1 atm = 760 mmHg (or Torr). Since the density of mercury is 13.59
g / cm3, finds that the mercury column of Torricelli's experience, whose section is 1 cm2,
weighs 1032.84 g = 1.033 Kgr: and this, in fact, is the weight with which the atmosphere
affects one square centimeter, also corresponding to the pressure by 101325 Pascal.
In gaseous systems the pressure is due to a rapid sequence of pulses produced by the impact
of the gas particles against the walls of the vessel
1 bar = 105 Pa
Temperature:
It is a measure of the tendency of heat to leave a body, related to the translational and
vibrational kinetic energy of the molecules. The concept of temperature is often related to the
subjective sensation of hot and cold, but the objective measurement of temperature is made
through thermometers. The most common instrument exploits the phenomenon of thermal
expansion, the most used substance is mercury, and the most used thermometric scales are
the following :
• Celsius ( centigrade): Anders Celsius (1701-1744), Zero is fixed at the melting
temperature of the ice while the boiling temperature of water is set at 100
• Fahrenheit: Daniel Gabriel Fahrenheit (1686-1736). Inventor of the alcohol

thermometer and mercury thermometer. Zero is fixed at the temperature of a mixture
of water and ice. The boiling temperature of water is set equal to 212 ° while that of
melting ice is set equal to 32 °
• Kelvin (absolute).
Here are some conversion formulas :

K = °C + 273.15
°F = 32 + 1.8 °C
°C = (°F - 32)/1.8
ome interesting temperatures (expressed in Kelvin):
Temperature Notazione o Fenomeno osservato
1 10-6 K Lowest temperature reached

4.2 K Liquefaction point of Helium

Liquefaction point of hydrogen
20 K
77 K Liquefaction point of nitrogen
273 K Solidification point of the water
373 K Boiling point of water
GAS
Gas is the simplest chemical system as the behavior of the gases in particular conditions does not
depend on the type of gas being examined. In fact, it has been seen experimentally that at low
pressures the behavior of any gas can be assimilated to that of an ideal gas thought of as a set of
molecules completely free to move without any interaction and considered in a very large volume
with respect to which they can be considered point-like.
.
Law of Boyle and Mariotte
The law of Boyle and Mariotte states that in conditions of constant temperature the pressure of an
ideal gas is inversely proportional to its volume, that is, that the product of the gas pressure and the
volume it occupies is constant.
This constant is a function (increasing) of the absolute temperature, the nature of the gas and the
number of moles.
The law can also be written with the following more complete notation:
in which it is indicated that the constant varies with temperature and that the law holds at constant
temperature.

The law of Boyle and Mariotte is experimentally verified for gases that behave like an ideal gas, or
for gases in conditions of not too high pressure (rarefied gas) and temperatures not too close to the
liquefaction temperature.
Boyle and Mariotte's law can be expressed as:
where V1 and V2 represent the values of the volume assumed by the gas in an isothermal
transformation during which the pressure passes from the value p1 to the value p2. The subscripts
"1" and "2" therefore indicate the thermodynamic state of the gas before the transformation and
after transformation, being T1 = T2
Scuba diving
The law of Boyle and Mariotte constitutes one of the foundations on which the technique and
technology of diving rests. In fact, the behavior of a gas (in this case air or mixtures) is a function of
the hydrostatic pressure to which it is subjected and the modifications of its volume show the
practical application of the law. The classic example is the pneumatic diving bell consisting of a
hollow cylinder inside and full of air with the lower end open which is lowered vertically into the
water at progressively increasing depths. At a depth of 10 meters the ambient pressure doubles,
passing from 1 bar of the surface to 2 bar, the water then penetrates into the bell reducing the
volume of the air contained in it by half. To have an equal reduction in air volume (i.e. 1⁄3 of the
original volume), the bell must therefore be lowered to a depth of 30 meters, where the pressure is 4
bar (1 bar of the surface + 1 bar for every 10 meters).
1 bar= 105 Pa
Gay-Lussac's first law or Charles's law
Gay-Lussac's first law, also known as Volta's Gay-Lussac law, states that under conditions of
constant pressure, the volume of a gas increases linearly with temperature.
By indicating with V0 the volume of the gas at a temperature of 0 ° C and with V (T) the volume at
a temperature T> 0, this law is mathematically expressed by the relation:]
T in °C.
The parameter α is called the gas expansion coefficient and is valid for all gases about 3.663 10−3 °
C −1, equal to about 1/273 ° C − 1 (the dimensions of α are ° C −1 because the product α T must be
dimensionless). α therefore represents the increase in volume undergone by a unit volume of gas
when its temperature increases by 1 ° C.
For example, if the gas temperature increases from 0 to 100 ° C, the volume of the gas at 100 ° C is
V (100) = V0 (1 + 0.3663) = 1.3663 V0; that is, the volume of the gas increases by about 36%. If
the temperature is reduced to values below 0 ° C, then the volume V (T) is proportionally reduced;
the equation predicts that the volume V vanishes at a temperature T = -1 / α = −273.15 ° C.
E. Angelini – DISAT – Politecnico di Torino - 10 -
This temperature is called absolute zero. In reality, most gases liquefy before reaching this
temperature: nitrogen at −196 ° C, hydrogen at −253 ° C. However, helium liquefies only at −269 °
C and follows the Gay-Lussac law around that temperature.
If the absolute temperature scale (Kelvin scale) is used, then Gay Lussac's first law takes the
simplest form
T in K.
Gay Lussac's first law is experimentally verified for not too high pressures and for temperatures not
too close to the gas liquefaction temperature, that is when the gas behaves like an ideal gas.
Second law of Gay-Lussac
Gay-Lussac's second law states that in conditions of constant volume the pressure of a gas increases
linearly with temperature.
Indicating with P0 the pressure of a gas at a temperature of 0 ° C and with P (T) the pressure at a
temperature T> 0, this law is mathematically expressed by the relation:
P (T) = P0 (1 + a T)
T in °C.
Graphical representation that alpha is always the same for any transformation, both isochoric and
isobaric.

The parameter α is called the gas expansion coefficient and is valid for all gases about 3.663 × 10-3
° C -1, equal to about 1/273 ° C-1. (The dimensions of α are ° C-1 because the product α t must be
dimensionless).
α therefore represents the relative pressure increase undergone by the gas when its temperature
increases by 1 ° C. For example, if the gas temperature increases from 0 to 100 ° C, the gas pressure
at 100 ° C is P (100) = P0 (1 + 0.3663) = 1.3663 P0; that is, the gas pressure increases by about
36%. If the temperature is reduced to values below 0 ° C, then the pressure P (T) is proportionally
reduced; the equation predicts that it vanishes at a temperature T = -1 / α = -273.15 ° C .
If the absolute temperature scale (kelvin scale) is used, then Gay Lussac's second law takes the
simplest form: :
P (T) = P0 a T
T in K.
Avogadro's law
Avogadro's law (sometimes referred to as Avogadro's hypothesis or Avogadro's principle) is a gas
law bearing the name of Amedeo Avogadro, who, in 1811, hypothesized that two given samples of
an ideal gas, at the same temperature, pressure and volume, they contain the same number of
molecules. Thus, the number of molecules or atoms in a specific volume of the gas is independent
of their size or the molar mass of the gas. As an example, equal volumes of molecular hydrogen and
nitrogen contain the same number of molecules, when they are at the same temperature and
pressure, and observe the behavior of ideal gases. In practice, real gases show small deviations from
ideal behavior and the law holds only approximately, but it is still a useful approximation for
scientists.
where:
V gas volume
n mole numbers
K proportionality constant
The most significant consequence of Avogadro's law is that the constant has the same value for all
ideal gases.
where :
p gas pressure
T temperature in kelvin
A common rearrangement of this equation is to denote by R the constant of proportionality, and

rearranging in this way:
PV = n R T

This equation is known as the ideal gas law.
By defining the standard conditions of temperature and pressure 1 atm (101.325 kPa) and 0 ° C
(273.15 K), the volume of one mole of gas can be found:
In the gas state equation:

• p is the gas pressure value;
• V is the volume occupied by the gas;
• n are the moles of gas;
• R is the universal constant of gases universal constant of gases, the value of which varies
according to the units of measurement adopted to express the other quantities in the equation;
• T is the absolute temperature of the gas, expressed in kelvins.
The value of R in the International System is:
sometimes in calculations, especially in chemistry, the value of

di:
Amedeo Avogadro
Lorenzo Romano Amedeo Carlo Avogadro was born in Turin on 9 August 1776 to Filippo, count of
Quaregna and Cerreto, high magistrate and then senator of the kingdom of Sardinia. Also initiated
into legal studies, he obtained a degree in law in Turin in 1795 and the title of doctor of
ecclesiastical law in 1796. Although he subsequently held various public legal-administrative
offices, he devoted himself to the favorite study of physical and mathematical sciences and for some
years he followed the courses of the physicist AM Vassalli-Eandi (1761-1825). In 1803 and 1804 he
presented to the Academy of Sciences of Turin, together with his younger brother Felice, two
memoirs, which remained handwritten: one on electricity, the other on the salt bond. In 1806 he was
entrusted with the post of physics repeater in the Regio Collegio delle Provincie and in 1809 that of
professor of `positive philosophy '(mathematics and physics) in the Regio Collegio (high school) of
Vercelli. During this period he published his two most famous works in Lametherie's Journal. In
1811 he published the Essai d'une maniere de determiner les masses relatives des molecules
elementaires des corps, et les proportions selon lesquelles elles entrent dans ces combinasions in
which he introduced a clear distinction between the concept of atom and molecule that allowed him
to reconcile the Dalton's ideas (leading to Avogadro's principle) with Gay-Lussac's observations. In
the second memoir of 1814, Avogadro's principle is expressed in evident form: Equal volumes of
gaseous substances, at equal temperature and pressure, represent the same number of molecules, so
that the densities of the different gases are the measure of the masses of their molecules and the
ratios of the volumes in the combinations of gases are nothing but the ratios between the numbers of
molecules that combine to form compound molecules. In 1819 he was appointed ordinary member
of the Academy of Sciences of Turin and in 1821 he became a member of the Accademia dei XL.
From 1820 to 1822 he held, at the University of Turin, the first Italian chair of `sublime physics'
(mathematical physics), until it was suppressed by the Piedmontese government for political
reasons (July 1822). Avogadro had the title of emeritus professor and a modest pension. In 1824 he
was appointed auditor in the Royal Chamber of Accounts as jurisconsult. The chair in Turin was
restored only in 1832 and entrusted to A.L. Cauchy, but in 1834 it was returned to Avogadro who
held it until 1850. Among other public offices, Avogadro was president of the Weights and
Measures Commission in whose capacity he had the merit of introducing the metric system in
Piedmont. He died in Turin on July 9, 1856.
Avogadro's number NA = 6.03 1023 is the number of atoms contained in 1 g of hydrogen. NA

constitutes the link between macrophysics and microphysics, allowing the masses of atoms to be
calculated in units of mass and not only in relative terms.
1 mole = quantity of matter containing a number of objects equal to Avogadro's number.
Grammomolecule = mass in grams of a mole of objects
The mass of 1 mole of H contains NA atoms of H and weighs 1 g
The mass of 1 mole of H2 contains 2 NA atoms of H and weighs 2 g
The mass of 1 mole of O2 contains NA O2 molecules and weighs 32 g this because an oxygen
molecule weighs 32 times the weight of an H atom.
Number of moles n = N / NA, where N is the number of molecules M = molecular mass.
The perfect gas model is based on the following two assumptions:

i. The gas molecules are rigid, point-like spheres
ii. The interaction energy between the molecules is zero
We will see how the failure of these hypotheses affects the behavior of a real gas. To analyze
the non-ideal behavior of a real gas, the compressibility factor Z can be examined.
For the perfect gas Z = 1, in fact, by the general law of the perfect gas, the ratio between PV and
nRT is equal to 1.
All real gases behave abnormally, but tend towards the ideal (Z = 1) when P approaches 0 and when
their T is high. For most gases the compressibility ratio tends to be less than 1 at low pressures. This
means that that given real gas is more compressible than a perfect gas would be and this suggests
the existence of intermolecular forces of an attractive type such as to favor gas compression. A
compressibility factor greater than 1 (typically at high pressures) is instead an indication of the
presence of intermolecular repulsive forces at short range of action such as to oppose compression.
As the temperature increases, the minima of the curves become less and less marked, until for
sufficiently high temperatures (the exact value of which depends on the gas) the compressibility
factor is always greater than 1.
Real gases satisfy the equation of state of the perfect gas when one of the two (or both) of the
following conditions occur :
Low density: P → 0
High temperature
Real gases don't always perform ideally, especially at low temperatures and / or high pressures.
The reasons for this deviation from ideality are determined:
1. by the presence of interaction forces between particles (van der Waals forces);
2. from the real physical dimensions of the particles so that in real gases the volume materially
occupied by the molecules is not negligible compared to the volume of the container in which the
gas is contained
Van der Waals modified the equation of state of the ideal gas in relation to take into account the two
essential differences between ideal and real gas:
The structural model of real gases takes into account that, if a real gas is cooled to a sufficiently
low T, it condenses (the ideal gas does not), becoming liquid or solid; at T = 0 K the solid will have
a volume b: therefore the total volume available to the gas is not V, but (V - b) where b is the molar
volume of the gas at 0 K.
Furthermore, in real gas, the motion of the particles is not uniform: there are attractions and
repulsions, especially when the particles are close (before and after a collision).
This leads to a decrease in P compared to the ideal: Pideal = P + (a / V2)

in which the term a / V2 is called internal P, or cohesion and is a factor related to the intermolecular
interaction forces.
The structural model of real gases takes into account that, if a real gas is cooled to a sufficiently low
T, it condenses (the ideal gas does not), becoming liquid or solid; at T = 0 K the solid will have a
volume b: therefore the total volume available to the gas is not V, but (V - b) where b is the molar
volume of the gas at 0 K. Moreover, in the real gas, the motion of the particles is not uniform: there
are attractions and repulsions, especially when the particles are close.
The equation for real gases, called Van der Waals therefore becomes:
(P + n2a / V2) (V-nb) = nRT
the factor n depends on the fact that the number of particles must be taken into account (note that n /
V represents the concentration).
The pressure measured experimentally for a real gas is always less than the value obtained from the
ideal gas equation. The difference is all the more evident the greater the density of the gas, i.e. at
high pressures and / or low temperatures. Increasing the pressure leads to a reduction in the average
distance between the particles and therefore an increase in the forces of interaction. Decreasing the
temperature means making the molecules slower and therefore more sensitive to the weak forces of
interaction. If two molecules of a real gas are progressively approached, attractive forces first arise,
then, as the distance decreases, the repulsive forces become sensitive which, subsequently, balance
and overcome the attractive forces. In the field of applicability of the van der Waals equation, the
distances between the molecules are such that it is always in the field of attractive forces. Once
again, the mutual intermolecular forces of attraction (which we will see in more detail below)
become sensitive when the density of the gas in molecules per unit volume (n / V) is high. In these
conditions, crowding is greater and the distance between the molecules is smaller. The
intermolecular attraction forces decrease the frequency of the impacts against the vessel walls and
therefore the real pressure exerted by the gas is less than the ideal one. Molecular cohesion slows
down the outermost molecules of the gaseous mass, thereby making collisions against the walls less
frequent and on average less violent.
The equation for real gases, called Van der Waals therefore becomes:
(P + n2a / V2) (V-nb) = nRT
the factor n depends on the fact that the number of particles must be taken into account (note that n /
V represents the concentration).

Depending on whether the effect of volume (with effect + DP) or that of cohesion forces (with
effect -DP) predominates, the P of a real gas will be greater or less than that of the ideal gas. At high
T the effects of cohesion are less (since the kinetic energy of the particles predominates), while at
high P the volume available for motion decreases a lot (part of it is in fact occupied by the
covolume b of the particles, which we can only neglect low pressure). In the calculations for real
gases, the general law is normally used, since in normal environmental conditions it is quite
reliable.
Parameters a and b are characteristic of each gas and are measured experimentally.
An estimate of the parameter b is provided by the measurement of the molar volume of the
compound in the liquid state. Note that if the gas is very rarefied, that is, if the volume is large, the
corrective terms introduced become negligible and the van der Waals equation tends to the equation
of state of the perfect gas. The value of the internal pressure is completely negligible in relation to
that of the actual pressure at normal pressure and temperature conditions, it cannot be neglected,
even in first approximation evaluations, when the pressure becomes very large and the temperature
very low. For air under pressure of 1 atm, the internal pressure is only 0.0028 atm at 0 ° C, and
0.0056 atm at -75 ° C. But under a pressure of 100 atm, the internal pressure is 26 atm at 0 ° C, and
84.5 atm at -75 ° C.
The value of the covolume, different from gas to gas, averages around 30 cm3 / mol, therefore it
corresponds to about 0.15% of the volume occupied by a mole of gas under standard conditions of
pressure and temperature (1 atm, 0 ° C). It can be assumed that the covolume corresponds
approximately to four times the total volume of the 6,022 1023 molecules contained in a mole.
This table shows the values of the Van der Waals constants for some substances.
,
a (L2bar/mol2) b (L/mol) a (J·m3/mol2) b (m3/mol)

Hydrocloric acid 3,716 0,04081
Sophidric acic 4,490 0,04287
Water 5,536 0,03049
Ammonia 4,225 0,03707
Argon 1,363 0,03219
Nitrogen 1,408 0,03913
Benzene 18,24 0,1154
Carbon dioxide 3,640 0,04267 0,3640 0,00004267

Buthane 14,66 0,1226

Chlorine 6,579 0,05622
Clorobenzene 25,77 0,1453
Chloroethane 11,05 0,08651
Chloromethane 7,570 0,06483
Stannic Chloride 27,27 0,1642
Nitrogen Dioxide 5,354 0,04424
Helium 0,03457 0,0237
Exane 24,71 0,1735
Ethandiol 11,39 0,08098
Ethane 5,562 0,0638
Ethanol 12,18 0,08407
Dietil ether 17,61 0,1344
Freon 10,78 0,0998
Hydrogen 0,2476 0,02661
Iodobenzene 33,52 0,1656
Kripton 2,349 0,03978
Mercury 8,200 0,01696
Methane 2,283 0,04278
Methanol 9,649 0,06702
Carbon Monoxide 1,505 0,03985
Neon 0,2135 0,01709
Nitrogen Oxide 1,358 0,02789
Oxygen 1,378 0,03183
Propane 8,779 0,08445
Nitrogen Protoxide 3,832 0,04415
Carbon Sulphide 11,77 0,07685
Tetracloruro di carbonio 19,7483 0,1281
Toluene 24,38 0,1463
Xenon 4,250 0,05105
Comparison between the Van der Waals law and the perfect gas law
Low pressure
If the gas pressure is not too high, the Van der Waals model and the perfect gas model do not differ
much. This is due to the fact that:
• the excluded volume b is negligible with respect to V; for example, in the case of CO2, b = 43cm³,
while the standard molar volume (at 0 C and 1 atmosphere) is equal to 22414cm³;

• the distances between the molecules are large enough to make the term a / V² substantially null.
Again in the case of CO2, the term a / V² represents only 7 per thousand of the atmospheric
pressure.
In these cases the equation of state of the ideal gases represents a good approximation of the "real"
gas.
Medium and high pressures
If the gas pressure is higher, however, significant differences are observed between the two models
(see the graph, again relating to CO2):
• in the area of medium pressures, between 5 and 15 MPa (50-150 atm) the volume V decreases
sufficiently to make the weight of the term a / V² be felt; this means that the forces of attraction
between the molecules are no longer negligible and have the effect of reducing the pressure with
respect to the hypothetical perfect gas in which the molecules do not interact.
• In the high pressure area, greater than 15 MPa, the volume has reduced to the point that b is no
longer negligible compared to V; in this way the expression V - nb becomes a significantly smaller
number than V, with relative pressure increase and "overtaking" of the Van der Waals curve with
respect to that of ideal gases
Liquefaction of gases
The van der Waals law allows us to understand the gas liquefaction process well. For each gas there
is a TC temperature, called critical temperature, which in a certain sense represents the "frontier" of
the liquefaction process:
• if T> TC it is not possible to liquefy the gas, even by compressing it at very high pressures;
• if T <TC it is possible to liquefy the gas if it is compressed up to a suitable pressure, which is
lower the lower the temperature. The figure shows the isotherms of carbon dioxide at different

temperatures, according to the provisions of the Van der Waals law (remember that for the ideal gas
law these curves would simply be the hyperbolas of Boyle Mariotte's law, pV = cost).
For CO2 TC = 31°C = 304 K.

• La curva a 70 C è ancora simile ad un'iperbole (anche se la pressione è più bassa di quella
calcolabile con la legge di Boyle);
• a 40 C si nota un intervallo in cui la curva cambia il verso della concavità (sono presenti
due punti di flesso); in entrambi i casi comunque il CO2 rimane in fase gassosa per ogni
valore di pressione.
• La curva a 31 C illustra cosa succede nelle condizioni critiche. Quando il gas viene
compresso in modo tale da raggiungere il volume critico VC,e la corrispondente pressione
critica pC, diventa liquido (il CO2 è gassoso per V>VC e liquida per V<VC).
• Le curve a 13 C e 21 C rappresentano solo parzialmente il comportamento reale del gas (in
queste condizioni si raggiungono quindi i limiti di validità dell'equazione di Van der Waals).
Il tratto di destra delle curve (corrispondente alle pressioni minori) descrive in modo
adeguato il comportamento del gas, mentre la loro parte centrale (dove si osservano le
"gobbe") non corrisponde alla realtà fisica, in quanto il gas, invece di seguire la curva che
indicherebbe un assurdo aumento del volume all'aumentare della pressione, segue il
"plateau" indicato dalla linea nera orizzontale L. La linea di plateau viene posizionata ad
un'ordinata tale che l'area compresa tra la linea e il fosso sia uguale a quella compresa tra la
linea e la gobba. In questa zona avviene la liquefazione del gas, per cui al termine del
"plateau" troviamo soltanto CO2 liquida se si tenta di ridurre ulteriormente il volume, la

pressione aumenta in modo molto rapido, dal momento che i liquidi sono praticamente
incomprimibili. Osserviamo infine che la lunghezza del plateau aumenta al diminuire della
temperatura.
Per ottenere il punto Tc = (Vc; pc), possiamo porre che (dp/dV)T = 0 e ((d2p)/(dV)2 )T = 0. tenendo
presente che l’equazione di van der Waals può essere riscritta isolando p, ottenendo così un sistema
di equazioni dalle quali ricavare Tc e Vc. − RTV − b − 2 + 2aV − 3 = 0,2 RT(V − b) − 3 − 6aV − 4 =
0 (Vc = 3b RTc = 8a/27b). Sostituendo questi valori nell’equazione di van der Waals, riarrangiata,
otteniamo pc = a/(27b2). Noti questi valori, è possibile trovare il fattore di compressibilità critico zc
= 3/8. Infine possiamo trovare i parametri a e b:
b = RTc/8pc
a = (27R2 Tc2)/(64pc).
Queste relazioni permettono di determinare le costanti a e b per i vari gas da una misura
sperimentale di pC e TC (la misura sperimentale di VC risulta più difficile).
KINETIC THEORY OF GAS
In the second half of the nineteenth century Maxwell and Boltzmann were able to formulate a
coherent description of the behavior of matter and energy by applying a theory called Statistical
Mechanics. The assumption underlying statistical mechanics is that, since material systems are
composed of an enormous number of elements (atoms or molecules), it is not possible, for practical
reasons, to apply the laws of classical mechanics to individual particles, calculating the position for
each , the speed and energy of each particle. However, it remains of great importance, managing to
demonstrate that the macroscopic variables that describe the external state of matter, such as
volume, pressure and temperature, can be linked to microscopic variables that describe the dynamic
behavior of individual particles, such as kinetic energy. average, the frequency of collisions
between particles etc. It is possible to describe such systems by taking into consideration the
average values assumed by the dynamic and kinematic variables involved. In other words, this
theory is a statistical description of the dynamic and kinematic properties of the aggregates of
particles that make up a material system. Statistical mechanics has arrived in this way to obtain
results That part of statistical mechanics that describes the disordered motion of gaseous particles is
commonly referred to as the kinetic theory of gases.
The kinetic theory applies to ideal gases and is therefore only valid if the following conditions are
met:
1) The volume of the particles (covolume) is negligible compared to the volume of the gas.
2) Intermolecular forces are negligible
3) the chaotic motion of the particles produces collisions with each other and with the perfectly
elastic walls of the container.
The kinetic theory of gases is above all capable of interpreting two fundamental macroscopic
phenomena at the molecular level: the pressure exerted by a gaseous mass and its temperature.
Trying to simplify the discussion, it can be asserted that the pressure exerted on a wall of the
container by the gas is the effect of the collisions on the wall of the gas particles (atoms or
molecules). The pressure is nothing more than a force applied on a certain surface, this same force
therefore derives from the sum of the variations in the momentum of a particle during each single
impact on the wall. In fact, according to a fundamental principle of physics, every applied force
corresponds to a variation of momentum in a system and vice versa. A single particle in a gas
receives a very large number of collisions with other particles during even very short times. These
collisions deflect its trajectory, as shown in the figure, and cause the speed of the particle and
therefore its kinetic energy to change continuously over time. We can therefore define time-
averaged quantities, such as the average velocity and average kinetic energy of the particle.
Considering that in even a small mass of gas (a few grams) there are numerically very high
quantities of particles (1021-1023) if we fix a certain instant we can also observe a statistical
distribution of the velocities over the set of particles. In this way it is possible to define averaged
quantities in space, such as average velocity and average kinetic energy, which correspond exactly
to those defined above as temporal average.
Computer simulated trajectory of a gas particle in 160 nanoseconds
The temperature of a gas is closely related to the kinetic energy (½mv2) of its particles. This
dependence is so close that the only effect of this thermodynamic variable in a gaseous mass is to
increase the total kinetic energy of the set of gaseous particles. This increase in kinetic energy is
proportional to the increase in temperature if the temperature is measured starting not from an
arbitrary zero (such as zero centigrade, Celsius scale) but absolute (Kelvin scale). In other words,
we must imagine starting with the heating from zero kelvin (-273.15 ° C) when the thermal
agitation is zero and therefore the total kinetic energy is zero (each particle can be considered
immobile even if strictly speaking the state gas would cease to exist under these conditions) and
therefore if T (kelvin) = 0 also E (kinetics) = 0. It can then be shown, on the basis of the
proportionality mentioned above, that the total kinetic energy of the gaseous mass is proportional to
the absolute temperature (in kelvins). Now let's see how the temperature, pressure and volume of a
gas can be linked together. Imagine that N particles of mass m are contained in a cubic vessel
whose side measures l.

Let us assume that the gas in question is ideal in the sense that the molecules have a negligible size
with respect to the distance that separates them, that no attractive or repulsive forces of any kind are
exerted between them and that the reciprocal collisions between the particles or between them and
the walls are perfectly elastic. According to the Boltzmann statistics, the molecules will move at
different speeds and in different directions; the velocity of a particle, like any vector, can be
decomposed according to three orthogonal directions, which we make coincide with the sides of the
cube. Called v the velocity of the particle, vx, vy and vz will be the three components according to
the three orthogonal directions. However, it becomes obvious that the modulus (length) of the
vector vx is less than v. If we mediate on a very large number of particles it can be shown that the
component of the average velocity along the x direction is, in intuitive analogy with the ratio
between the internal diagonal of a cube (v) and its side (vx): Vaverage = √3v (average_x)
Let us now calculate the statistical frequency with which a particle (with velocity v) hits one of the
two faces of the cube perpendicular to the x direction. The number of collisions per unit of time
(frequency) will be given by vx / 2l, as a particle travels along the x axis a path 2l between one
collision and the other and also moves along that axis with its own speed (relative to that axis) vx.
Since collisions are admitted to be perfectly elastic, the molecule will bounce off the wall with
velocity - vx without undergoing changes in kinetic energy. The momentum along the x axis, which
before the collision was m vx, after the collision will be -m vx (the other components of the
momentum m vy and m vz do not change during the impact with the wall). The total variation of the
momentum will therefore be 2mvx. For N molecules in the vessel the overall variation will
obviously be 2 · N · m · vx (average). If we multiply this value by the number of collisions per
second for a particle (vx / 2 l) we will obtain the total variation of the momentum, equal to:
Δ total momentum = N m vx (average) 2 / l = 1/3 N m vx (average) 2 / l
From the fundamental laws of physics it is known that the variation of the momentum corresponds
to the applied force, in our case the pressure P multiplied by the area (l2) of the face of the cube for
which we have:
P l2 = 1/3 N · m · u2 / l
from which bringing to the left remembering that l3 is the volume of the container, we have
PV = 1/3 N m v2
where v indicates the average speed of the molecules or more precisely the average square speed.
Recalling that the average kinetic energy is proportional to the absolute temperature in kelvins, we
can also write:
P V = 1/3 N m v2 = cost T
This is the fundamental equation of the kinetic theory of gases.

We will see shortly how the heat of the proportionality constant can be obtained.
The molecules of a gas are in a situation of continuous motion and each of them, fixed at a certain
instant, has a certain speed and therefore a certain kinetic energy. Due to the numerous collisions
between the gas molecules (even 1010 collisions per molecule per second at ambient temperature
and pressure) there is a continuous transfer of kinetic energy between one molecule and another and
therefore the kinetic energies of the molecules are different and continuously variable over time. J.
Maxwell calculated the statistical distribution of kinetic energies between the molecules of an ideal
gas at constant temperature and pressure.
The resulting curve has the form of an asymmetric Gaussian and his equation gives us the
probability that a molecule has kinetic energy E (ie the fraction of molecules with kinetic energy E)
as a function of the kinetic energy E itself.
prob (E) = 2 / √ π (1 / kT) 3/2 exp (-E / kT) √E
where k is Boltzmann's constant and R (universal gas constant) divided by Avogadro's number
(NA).
This famous equation does not contain the molecular weight of the gas and is therefore valid for any
gas that behaves in an ideal way.
.

Distribution of the kinetic energy E for an ideal gas
The most probable value of the kinetic energy obviously corresponds to the maximum of the
Maxwell function and is obtained for E = kT / 2 while the average value of the energy, which does
not correspond to the most probable value, is obtained for E = 3kT / 2. By integrating the Maxwell
curve it results that the fraction of molecules (N / Ntot) with energy higher than a certain value (Ea)
is expressed with a good approximation by a rather simple mathematical relationship:
N / Ntot = exp (-Ea / kT)
Ea refers to a single molecule and k is Boltzmann's constant (k = R / NA = 1.38065 10-23J K-1)
The Maxwell distribution can also be expressed as a function of the speed of the particles, but in
this case the distribution function depends on the molecular weight of the gas. The following figures
show three graphic examples: the first refers to nitrogen and shows highlighted in black the part of
the curve that represents the molecules with a speed higher than 1200 m / sec at 500 ° C, while the
second and third curve they refer to helium and argon but at three different temperatures.

Distribution of the rates in two gases (He and Ar) at three different temperatures
The shape and position of the curve with respect to the axes depends on the values of the
temperature and molar weight of the gas. For example, we can see how the most frequent speed (but
also the average speed and the quadratic speed) is proportional to the ratio T / PM. As the molar
weight increases, the curve shifts to the left (towards lower speeds).
Thus at the temperature of 20 ° C the hydrogen molecules (Pm = 2) travel at an average speed of
1760 m / s, the oxygen molecules (Pm = 32) at 440 m / s, while the carbon dioxide molecules (Pm =
44) at an average speed of 375 m / s.
Changes in temperature produce the opposite effect. As the temperature increases, the curve shifts
to the right and the molecules therefore have a higher speed on average.
As you can see, the movements of the curve horizontally are accompanied by variations in the
amplitude of the curve itself. When the maximum of the curve moves to the left (low average
velocities) the particles have less dispersed velocity values, concentrating in a narrower range.
Conversely, when the maximum of the curve moves to the right (high average velocities) the
particles have more dispersed velocity values, distributed over a greater interval.
Graham's law
Graham's law, also Graham's law of effusion, was formulated by Thomas Graham experimentally
discovered that the effusion rate of a gas is inversely proportional to the square root of the
molecular mass of its constituent particles. The formula can be written as:
Where is it:
• V1 is the effusion rate of the first gas.
• V2 is the effusion rate of the second gas.
• M1 is the molar mass of the first gas.
• M2 is the molar mass of the second gas.
Graham's law is as valid for outpouring as it is for diffusion. Graham's law is valid when the mean
free path is greater than the diameter of the capillary hole through which the gas pours. If this does
not happen, the molecules collide near the hole and the lack of bumps on the side of the hole pushes
the gas out of the container. The diffusion rate in a liquid is also directly proportional to the
solubility coefficient.
Where is it:
• V1 is the effusion rate of the first gas.
• V2 is the effusion rate of the second gas.
• M1 is the molar mass of the first gas.
• M2 is the molar mass of the second gas.
Graham's law is as valid for outpouring as it is for diffusion. Graham's law is valid when the mean
free path is greater than the diameter of the capillary hole through which the gas pours. If this does
not happen, the molecules collide near the hole and the lack of bumps on the side of the hole pushes
the gas out of the container. The diffusion rate in a liquid is also directly proportional to the
solubility coefficient.
The enrichment process of natural uranium (235U = 0.72%; 238U = 99.28%;) is based on the different
effusion rate of the two gaseous substances 235UF6 and 238UF6 (uranium hexafluoride is a liquid that
boils at 56 ° C) Only the nucleus of the uranium isotope 235 undergoes nuclear fission The passage
of the gaseous mixture through a porous septum that separates two compartments that have different
pressure determines an enrichment of the lighter component (235UF6). The enrichment factor,
defined by the square root of the ratio between the masses of the two isotopic species (1.0043) is
small. However, by repeating the effusion process many times, it is possible to separate the two
isotopes. Approximately 340 steps are required to achieve a 3% enrichment. During the Cold War,
gaseous diffusion played a fundamental role as a technique for enriching uranium, although it has
now been completely replaced with new methods. The gas centrifuge uranium enrichment process
uses a large number of series rotating cylinders and parallel formations. This rotation creates a
strong centrifugal acceleration so that the heavier gas molecules containing 238U move towards the
outside of the cylinder and the lighter gas molecules with a higher concentration of 235U collect at
the center.
The gaseous mixtures
Gases respond to changes in pressure, volume and temperature all in the same way and this makes it
irrelevant to know if the molecules of the sample are the same or not. A mixture of gases that do not
react with each other behaves like a single pure gas. Dalton's law of partial pressures is the law that
states that: The total pressure exerted by an ideal mixture of ideal gases is equal to the sum of the
partial pressures that would be exerted by the gases if they were present alone in an equal volume.
The partial pressure pi of a component of a gas mixture is the pressure that this would have if it
occupied, by itself, the available volume of the entire mixture.
More precisely, the pressure P of a mixture of q gas can be defined as:
where pi represents the partial pressure of each component.

This means that each gas in an ideal mixture acts as if the other gas were not present and therefore
the pressures of each gas can simply be added together. It is assumed that gases do not react or
interact by intermolecular forces (Van Der Waals, London) with each other. Dalton's law is named
after the chemist John Dalton, who formulated it in 1807. Dalton's law can be extended in ideal
gases to the following relationship:
where:
• P: total pressure
• R: gas constant
• T: absolute temperature ( kelvin K)
• V: volume of the container
• n1, n2.. ni: moles of all the gases
In this sense, it is possible to calculate the total pressure even with variations in temperature and
volume. However, considering that:
Where
and knowing that the molar fraction xi is the ratio between the moles of the gas and the sum of the
moles of each gas, that is:
it follows that the partial pressure of each component is equal to the total pressure for its mole
fraction:
Amagat's law
Amagat's law (1880) states that the volume of a gaseous mixture at a given temperature and
pressure is the sum of the volume that the individual components would have under the same
conditions. This is experimental proof that volume is an extensive quantity.
In mathematical terms:
The law also states that the ratio between the single partial volume and the total volume is equal to
the mole fraction
Scuba diving
Dalton's law and the principles set out above are of fundamental importance in diving. In fact the
quantity of gas (mainly nitrogen and oxygen) dissolved in the blood is proportional to the
atmospheric pressure. This means that as pressure increases, the quantity of dissolved gases in the
blood also increases. So if hypothetically at the pressure of 1 atm (at sea level) there is a liter of
nitrogen dissolved in the blood, at 10 atm there will be 10 liters of nitrogen dissolved in the blood.
The hyperbaric chamber emulates an environment such as that of the seabed, subject to pressure and
simulating a "rise" (ie constantly decreasing the pressure) facilitates the rebalancing between the
dissolved gases and the external pressure.
THE AIR WE BREATHE

Air is a gaseous mixture which has the following composition:

Oxygen (O2)
It is a fundamental element for living beings. Almost all organic compounds, in fact, contain
oxygen to a greater or lesser extent. Furthermore, the development of differentiated multicellular
organisms (ie with tissues and organs) was made possible only by the appearance of O2 in the
atmosphere, produced by the first unicellular organisms capable of carrying out photosynthesis.
Only the oxidizing action of molecular oxygen, in fact, is able to make the energy content present in
organic compounds completely available, necessary to satisfy the considerable energy needs of
evolved organisms. For example, the complete oxidation by O2 of 100 g of Glucose with the
formation of Carbon Dioxide (CO2) and water (H2O), a process called Respiration, produces 380
kilocalories, while the transformation in the absence of O2 of the same amount of glucose lactic acid
(process called Lactic Fermentation) produces only 26 kilocalories. The percentage of O2 in the
atmosphere has reached a stationary level (about 21% of the atmosphere) due to the equilibrium of
the chemical and biological processes that make up the Oxygen cycle. Under 17%, humans can no
longer breathe. Oxygen has a very strong oxidizing capacity, it is the essential comburent in all
combustion processes. The atmospheric percentage is the optimal one: we can define Oxygen as the
active atmospheric component
Nitrogen (N2)
Colorless, odorless, non-flammable, chemically very stable, non-toxic gas. Nitrogen becomes
asphyxiating in case of excessive concentration in the air: the increase of its concentration in the air
causes in fact phenomena of increasing malaise, such as dizziness, headache, tingling in the
extremities of the hands and feet, difficulty in speech , difficulty in performing physical work,
progressive loss of sensitivity.
Argon (Ar)
Argon is a colorless, odorless, non-flammable, chemically stable, non-toxic gas. However, an
atmosphere containing Argon can become asphyxiating if its concentration is so high as to reduce
the availability of oxygen for breathing. Argon is inert and therefore not corrosive towards metals or
other materials. Since Argon has a higher density than air, it can accumulate in the gaseous state in
low, unventilated areas, replacing the normal atmosphere and making the air suffocating due to lack
of oxygen. We can therefore define Argon as an inerting component of the atmosphere.
Other gases
The remaining 0.1 percent of atmospheric air is composed of gases such as carbon dioxide (CO2),
water vapor (H2O) and ozone (O3), which, however, are in fact the ones that determine the
characteristics physics of the atmosphere and also its degree of 'reactivity'. The main gases in fact
(Oxygen, Nitrogen and Argon) have little or no ability to react with other compounds and the
chemical composition of the atmosphere remains almost constant with the altitude at least up to 100
Km. The same thing cannot be said for the minor components (ie those that are part of the
remaining 0.1 per cent) whose concentration varies with altitude, latitude and season. Superimposed
on these variations there may also be variations with very variable temporal inertia in the
concentration of gases, due to anthropogenic and natural activities. The acceleration that these
variations have undergone in recent years, especially due to anthropogenic activity, and the analysis
of the micro-components that fall within this small but very important percentage of the atmosphere
are at the basis of the problems linked to atmospheric pollution.

Henry law
Henry's law, formulated by William Henry in 1803, regulates the solubility of gases in a liquid. In
particular, it claims that: A gas that exerts pressure on the surface of a liquid enters solution until it
reaches the same pressure in that liquid as it exerts on it. Henry's law says that at constant
temperature, the solubility of a gas is directly proportional to the pressure the gas exerts on the
solution. Reached equilibrium, the liquid is defined as saturated with that gas at that pressure. This
state of equilibrium remains as long as the external pressure of the gas remains unchanged,
otherwise, if it increases, other gas will enter into solution; if it decreases, the liquid will be in a
situation of supersaturation and the gas will be released returning to the outside until the pressures
are balanced again. A mathematical expression of Henry's law can be the following: where P is the
pressure of the gas on the solution, C is the concentration of the gas in the solution and k is a typical
constant of each gas which correlates the pressure of the gas on the solution and its concentration,
for example:
• O2: k = 769.2 L · atm / mol
• CO2: k = 29.4 L · atm / mol
• H2: k = 1282.1 L · atm / mol
These values are valid for gases dissolved in water at 298 Kelvin; it should be noted that the value
of the coefficient k varies with the variation of the solvent and the temperature. A rise in
temperature, causing rise of the kinetic energy of the gas, causes a decrease in solubility due to the
effect of removing the gaseous molecules from the liquid phase.
An alternative definition of Henry's constant is as follows: P = kx where P is the partial pressure of

the gas above the solution, and x is the mole fraction of the dissolved gas. According to this
definition, at 298K the Henry constant takes the values:
• O2: k = 4.34 × 104 atm
• CO2: k = 1.64 × 103 atm
• H2: k = 7.04 × 104 atm
The speed with which a gas enters solution or is released varies according to the difference in
pressures (external and internal) and is conditioned by its molecular composition and by the nature
of the solvent liquid. The decompression phenomenon, if it occurs quickly (due to a sudden
decrease in the external pressure of the gas), is said to be tumultuous because it causes the
formation of numerous bubbles, as happens when we uncork a beer or a sparkling wine. A
fundamental aspect lies in the fact that each gas, as specified in the argument relating to the Law of
partial pressures, enters into solution or is released independently of what the other gases present
do.
Scuba diving
In our aerial life we are saturated with nitrogen for about one atmosphere, and we can consider any
pressure variations which instead become massive when we go down into the water (every 10
meters of liquid column adds an atmosphere to that that weighs on the surface of the sea). During
the descent the nitrogen that is inhaled increases its partial pressure in proportion to the external one
and, as the sentence says, it is transferred from the lungs to the blood and then to all tissues in liquid
form. This phase is called saturation, and ends when, having reached a certain altitude for a
sufficiently long period, the pressure of the inert gases inside the body is equal to the external one.
During the ascent the inverse phenomenon occurs: the excess nitrogen returns to the gaseous form,
passes through the venous system and is eliminated through breathing, asymptomatically, provided
that the correct ascent times and possible stops are respected. decompression. The example of the
bottle of sparkling wine is very fitting and is adopted by didactics all over the world: inside the
bottle of sparkling wine there is dissolved gas under pressure (CO2, in this case). When the cap is
removed the carbon dioxide returns to its gaseous state releasing a quantity of bubbles and tends to
escape violently from its container, "shooting" the cap. If this operation is done with extreme
caution, it is possible to avoid the leakage of the wine just like in the organism; carelessness and
imprudence can be paid dearly with arterial gas embolism. Once out of the water, the desaturation
will not be finished yet: for this reason a second dive will have to be faced with special tables that
take into account the residual nitrogen still present in our body.

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Chemistry – A.A.

Dipartimento di Scienza Applicata e Tecnologia - Politecnico di Torino

E. Angelini – DISAT – Politecnico di Torino -1-

States of aggregation and changes of state

Solids Liquids Gas

E. Angelini – DISAT – Politecnico di Torino -2-

E. Angelini – DISAT – Politecnico di Torino -3-

E. Angelini – DISAT – Politecnico di Torino -4-

International system of measurement

Prefix Symbol Value with

Mega M 1000000 = 106

kilo k 1000 = 103

etto h 100 = 102

none Fundamental unit 1

deci d 0.1 = 10-1

centi c 0.01 = 10-2

milli m 0.001 = 10-3

micro µ 0.000001 = 10-6

E. Angelini – DISAT – Politecnico di Torino -5-

• Fahrenheit: Daniel Gabriel Fahrenheit (1686-1736). Inventor of the alcohol

Here are some conversion formulas :

Temperature Notazione o Fenomeno osservato

1 10-6 K Lowest temperature reached

E. Angelini – DISAT – Politecnico di Torino -7-

4.2 K Liquefaction point of Helium

77 K Liquefaction point of nitrogen

273 K Solidification point of the water

373 K Boiling point of water

Law of Boyle and Mariotte

E. Angelini – DISAT – Politecnico di Torino -8-

Boyle and Mariotte's law can be expressed as:

Gay-Lussac's first law or Charles's law

Second law of Gay-Lussac

E. Angelini – DISAT – Politecnico di Torino - 11 -

A common rearrangement of this equation is to denote by R the constant of proportionality, and

E. Angelini – DISAT – Politecnico di Torino - 12 -

This equation is known as the ideal gas law.

In the gas state equation:

The value of R in the International System is:

sometimes in calculations, especially in chemistry, the value of

Avogadro's number NA = 6.03 1023 is the number of atoms contained in 1 g of hydrogen. NA

The perfect gas model is based on the following two assumptions:

This leads to a decrease in P compared to the ideal: Pideal = P + (a / V2)

E. Angelini – DISAT – Politecnico di Torino - 15 -

(P + n2a / V2) (V-nb) = nRT

(P + n2a / V2) (V-nb) = nRT

E. Angelini – DISAT – Politecnico di Torino - 16 -

a (L2bar/mol2) b (L/mol) a (J·m3/mol2) b (m3/mol)

E. Angelini – DISAT – Politecnico di Torino - 17 -

Buthane 14,66 0,1226

E. Angelini – DISAT – Politecnico di Torino - 18 -

Medium and high pressures

E. Angelini – DISAT – Politecnico di Torino - 19 -

For CO2 TC = 31°C = 304 K.

E. Angelini – DISAT – Politecnico di Torino - 20 -

KINETIC THEORY OF GAS

Computer simulated trajectory of a gas particle in 160 nanoseconds

E. Angelini – DISAT – Politecnico di Torino - 22 -

Δ total momentum = N m vx (average) 2 / l = 1/3 N m vx (average) 2 / l

This is the fundamental equation of the kinetic theory of gases.

prob (E) = 2 / √ π (1 / kT) 3/2 exp (-E / kT) √E

E. Angelini – DISAT – Politecnico di Torino - 24 -