Thermodynamics

Plan
 Introduction : Definitions of thermodynamics
 System, Process, State
 Open, Closed and Isolated System
 Definitions of Temperature, Pressure
 Heat, Work and Internal Energy
 Zeroth, First, Second, and Third Laws of thermodynamics
 Ideal gas and Analytical expressions
 Thermodynamic Potentials F* and G* and State equations
 Heat expression , Calorimetric and thermoelastic coefficients in thermodynamics
 Introduce the concept of a pure substance and the physics of phase-change processes
 Illustrate the P-v, T-v, and P-T property diagrams and P-v-T surfaces of pure substances.
 Determining thermodynamic properties of pure substances from tables of property data.
 Present some of the best-known equations of state

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 Thermodynamics
 Heat
 As we know that temperature is a measure of the ‘intensity of heat’. ‘Heat flows’ from a body at higher
temperature to one at lower temperature. (Like pressure is a measure of the intensity of ‘force applied by
matter’→ matter flows from region of higher pressure to lower pressure).

 That implies if I connect two bodies (A)-one weighing 100kg at 10C and the other (B) weighing 1 kg at
500C, then the ‘heat will flow’ from the hotter body to the colder body. But, temperature comes in two
important ‘technical’ contexts in TD:
it is a measure of the average kinetic energy of the constituent entities. It is the parameter which determines
the distribution of species across various energy states available.

 At low temperatures the lower energy levels are expected to be populated more, as compared to higher energy
levels. As we heat the system, more and more molecules will be promoted to higher energy levels.

Heat flow B
A direction
500C
10C
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 Thermodynamics
 Heat
Heat is the energy transferred between a system and its environment because of a temperature difference that exists
between them.
 Like any type of energy, the SI unit for heat is the Joule. Another
common unit is the calorie (cal), which is approximately the
amount of heat energy needed to raise one gram one degree
Celsius.
1 cal = 4,186 J

 The British thermal unit (BTU) is approximately the energy

needed to raise one pound of water one degree Fahrenheit.

1 BTU = 1055 J = 252 cal

Fig 3 : If the temperature of a system exceeds that of its

environment as in (a), heat Q is lost by the system to the
environment until thermal equilibrium (b) is established. If the
temperature of the system is below that of the environment (c)
heat is absorbed by the system until thermal equilibrium is
established.
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 Thermodynamics
 Specific Heat Equation
 Latent Heat Equation
The specific heat of a substance, or materiel is given
by : The word “latent” comes from a Latin word that means “to lie
Q = m C T hidden.” When a substance changes phases (liquid  solid or from
liquid  gas) energy is transferred without a change in temperature.
Q = thermal energy, m = mass, C = specific heat Q = m Lf Q = m Lv
T = change in temp
Q = thermal energy, m = mass, L = heat of fusion or
vaporization
Ex: The specific heat of silicon is 703 J / (kg · ºC).
L is the energy per unit mass needed to change the state
How much energy is needed to raise a 7 kg chunk of
of a substance from solid to liquid or from liquid to gas.
silicon 10 ºC ?

Ex: Lf (the latent heat of fusion) for gold is 6440 J / kg. Gold
melts at 1063 ºC. 5 grams of solid gold at this temp will not
become liquid until additional heat is added.

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 Thermodynamics
 Work
 Work (W) in mechanics is displacement (d) against a resisting force (F).
W=Fd
Where the Work has units of energy (Joule, J).

 Work can be expansion work (PV), electrical work, magnetic work etc. (many sets of stimuli and their
responses).

 Work is coordinated flow of matter.

 Lowering of a weight can do work
 Motion of piston can do work
 Flow of electrons in conductor can do work.

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 Thermodynamics
 Work
 In a closed system (piston in the example figure below), if infinitesimal pressure increase causes the volume to
decrease by V, then the work done on the system is :
dW reversible = ─ P dV

 The system is close to equilibrium during the whole process thus making the process reversible.

 As V is negative, while the work done is positive (work done on the system is positive, work done by the system
is negative).
If the piston moves outward under influence of P (i.e. ‘P’ and V are in opposite directions, then work done is
negative.

P
2
Fig 4 : Pressure P applied on a cylindrical
material which contained a Volume V of gas.
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 Thermodynamics
Type Caracteristiques
Isothermal The temperature of the system remained
constant and it is equal to temperature of the
exterior
Isobaric The pressure of the system remained constant
and it is equal to the pressure of the exterior
Isochoric The volume of the system remained constant
during the process
Adiabatic There is no exchange of a heat between the
system and the exterior

 At constant temperature and pressure, while a system undergoes a transformation, the intensive parameters
depend on the massic and molar proportion of all substances present in the system.

 On the other hand, the extensive parameters don’t depend on the properties of all substances present in the
system.

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 Thermodynamics lessons
Definitions of Internal Energy
 Internal Energy
The energy of a system of a large number of particles is divided in three parts :

• Kinetic energy Ek of translation, rotation given in a specific referentiel

• Potentiel energy Ep related in all the forces fields where the system is undergoing (Example : Pesanteur field,
magnetic field, electric field)

• Internal energy U wich is the matters of energy contained in the system. This energy is related to the mass,
temperature, composition, links between atoms of molecules, and intermolecular links or relations

E = Σ Ek+ Σ Ep+ U

 If during the process leading from a state 1 to a state 2 of the system, this system remained stable, and if the
variations of potentiel energy and kinetic energy is zero, then the variation of the energy of the system is the
same of the variation of internal energy

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 Thermodynamics
 Variation of Internal Energy
Internal energy is a function of a state and the variation during the process from a state 1 to a sate 2 ( 1→2) depends
only the initial and final state of the system. This variation is given as a sum of energies

∆12 𝑈 = (W+Q) 1→2

Q et W represent the amount of the heat and the sum of all other energies received by the system called work
during the process.

While an elementary process is taking place, infinitesimal variations of the internal energy, the work andthe heat
present in the system, only internal energy has a differential form :
𝑑𝑈 = 𝛿W+ 𝛿Q

∆12 𝑈 , W and Q are an algebric quantities and it is given on Joule as a unit of energy.

In the isolated system,

∆12 𝑈 = 0 .

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 Thermodynamics
Zeroth law of thermodynamic

T T
 The properties of many bodies change as we alter their temperature by
moving a substance from a refrigerator to a warm oven, (example the volume
of a liquid increases, a metal rod grows a little longer,…etc).
 Thermal equilibrium :
Two systems are said to be in thermal equilibrium if there is no net flow of heat
between them when they are brought into thermal contact.
 Two systems individually in thermal equilibrium with a third system are in
thermal equilibrium with each other.

Fig 4 : the thermoscope T and Body A are in thermal equilibrium. The

thermoscope T and body B are also in thermal equilibrium (a). When body A
and body B are putted in contact through a diathermal walls then they are in
thermal equilibrium with each other

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 Thermodynamics
First law of thermodynamics
 The energy conservation told us if there is a variation of the internal energy of a system, indeed we had also an
exchange of energy between the system which we study and the surrounding.

 While a finished process who took place from an initial state to a final state of the system: the internal energy variation
∆U is the sum of the work W, which is all the exterior forces (macroscopic) applied on the system and the thermal
energy (Q) exchange (microscopic) called also heat :
∆U = W+Q
 In a general case, we write this equation above as a sum of macroscopic energies of the system which varies during the
process :
∆( Ek + Ep + U) = W+Q
 This two equation explain the energy conservation : the total energy variation (macrocopic and microscopic) of a
system is equal to the energy exchange between the system and the surrounding.

While an elementary process is taking place, infinitesimal variations of the internal energy, the work and the heat present
in the system, only internal energy has a differential form :
𝑑𝑈 = 𝛿W+ 𝛿Q
∆𝑈 , W and Q are an algebric quantities and it is given on Joule as a unit of energy.

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 Thermodynamics
Second law of thermodynamics
 We call entropy of a system in an equilibrium state, the value
𝑆 = 𝑘𝐵 ln Ω
Where Ω is the number of micro realisations of a macroscopic state of the system during the process, and 𝑘𝐵 is
Boltzmann constant (𝑘𝐵=1,38 10-23 J.K-1). The entropy has the same unit or dimension as the Boltzmann constant. The
micro realisations has to be equiprobable.

 When the system is on a state of equilibruim, then we have a maximun of entropy compatible with the all exterior
forces applied on the system.

 When the applied force is taken off , the isolated system progress towards an equilibrium state. If the process is
irreversible then his entropy increase.

 The variation of entropy depends on the transformation, or process which the system undergoes. The entropy of a
system clearly mechanic is zero.

 the second law of thermodynamic is :

𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 ∶ ∆𝑆 = 0 ( 𝑆 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡)
• Isolated System
𝐸𝑣𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑖𝑟𝑟𝑒𝑣𝑒𝑟𝑠𝑖𝑏𝑙𝑒 ∶ ∆𝑆 > 0 (𝑆 𝑖𝑛𝑐𝑟𝑒𝑎𝑠𝑒)
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 Thermodynamics
Third law of thermodynamics
 For substances in internal equilibrium, undergoing an isothermal process, the entropy change goes to zero as T
(in K) goes to zero.
lim (∆𝑆) T→ 0 = 0

 The law is valid for pure substances and mixtures.

 Close to Zero Kelvin, the molecular motions have to be treated using quantum mechanics → still it is found that
quantum ideal gases obey the third law.

 Phenomenological description of the third law. There does not exist any finite sequence of cyclical process,
which can cool a body to zero Kelvin (absolute zero).

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 Thermodynamics
Ideal and Perfect gas
 In an ideal gas the molecules do not interact with each other (Noble gases come close to this at normal temperatures).
An ideal gas obeys the equation of state:
𝑃𝑉 =𝑛𝑅𝑇

Where P is the pressure, V the volume , n number of mol quantities, R is Universal gas constant (8,31 J/mol.K) and T the
temperature.
 As the molecules of a ideal gas do not interact with each other, the internal energy of the system is expected to be ‘NOT
dependent’ on the volume of the system.
𝜕𝑈
=0
𝜕𝑉 T
 A gas which obeys both the above equations is called a perfect gas.
 Internal energy (a state function) is normally a function of T & V: U = U(T,V).
 For a perfect gas: U = U(T) only.

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 Thermodynamics
Analytical equations

We consider a system which his equilibrium state is given by an internal energy U, the volume V, the number ni of
mol of each substance i, his entropy S(U,V, ni) lead to a partial derivation in terms of all the variables parameters.
Temperature is the value T given by :
1 𝜕𝑆
=
𝑇 𝜕𝑈 𝑉 , ni
Pressure P is the value P given by :
𝑃 𝜕𝑆
=
𝑇 𝜕𝑉 𝑈, ni
Chemical Potentiel of the substance i is the value 𝜇𝑖 given by :

−𝜇𝑖 𝜕𝑆
= 𝑈, V, nj, j ≠ 𝑖
𝑇 𝜕ni
While an infinitesimal process, the entropy S is given by :
dS =(1 𝑇) (dU + P dV ─ 𝑖 𝜇𝑖 dni)
In the same conditions, th internal energy is given by :
dU = TdS ─ P dV + 𝑖 𝜇𝑖 dni
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 Thermodynamics
Analytical equations
 For an open system, the number of particles change because of an importation of matter from the
surroundings. Consequently the entropy also change when the number of particles, substances
change.

 For a closed system, the quantities of each constituent in mol don’t change unless when there is a
transformation or transition between two state (phase) or when there is a chemical process.

 During a transformation of a closed system, there is only two parameters who varies, for example,
(internal energy and volume) , (entropy and volume), ….etc.

Closed system with or non modification of composition :

dS =(1 𝑇) (dU + P dV ) ou dU = T dS ─P dV

1 𝜕𝑆 𝑃 𝜕𝑆
= et =
𝑇 𝜕𝑈 V 𝑇 𝜕𝑉 U

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 Thermodynamics
The thermodynamic Potential F*
We consider a closed thermodynamic system. We name U his internal energy and S his entropy . We suppose that this
system undergoes a monothermal, isochoric and without a work done process. This system is with the contact with a
thermostat at temperature T0 . By his definition, the thermodynamic potential is the state function F*

F* = U ─ T0 S

 When the system undergoes a isothermal and isochoric process, the potential F become free energy or Free Gibbs
described by this equation :

F=U─T S

 The heat capacity of a thermostat is theorically unlimited, very high value.

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 Thermodynamics
Potentiel thermodynamic G*
We consider a closed thermodynamic system. We name U his internal energy, S his entropy and V his volume . We
suppose that this system undergoes a monothermal with the contact with a thermostat at temperature T0, monobaric with
the contact with a reservoir at exterior pressure P0 and without a work done process. By his definition, the thermodynamic
potential is the state function G*

G* = U ─ T0 S + P0 V

 When the system undergoes a isothermal and isobaric process, the potential G become Free enthalpy described by
this equation :

G = U ─ TS + PV

 We express the state function enthalpy H of the system by this equation described below :

H = U + PV

 And we notice that the thermodynamic potential G is also expressed by this formula :

G = H ─ TS
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 Thermodynamics
Calorimetric and thermoelastic coefficients in thermodynamics
 In thermodynamics, the calorimetric coefficients are coefficients allowing to express the heat absorbed by
a thermodynamic system undergoing a transformation without change of chemical composition nor phase
change according to the variables pressure, temperature and volume.

 The thermoelastic coefficients make it possible to express the variation of volume or pressure undergone
by the system as a function of these same variables and thus to establish the equation of state of a pure
body or a mixture.

 All these coefficients are related to the thermodynamics potentials which make it possible to establish
various relations between them, in particular the relations of clapeyron, the relation of mayerand the
relation of reech.

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 Thermodynamics
 Calorimetric Coefficients

 In a reversible transformation, the heat Q absorbed by a pure body or a mixture of constant composition can be
expressed using six calorimetric coefficients according to the variables followed during the transformation :

Calorimetric coefficients :

𝛿𝑄 = 𝑇𝑑𝑆 = 𝑛 𝐶𝑉 𝑑𝑇 + 𝑙 𝑑𝑉
𝛿𝑄 = 𝑇𝑑𝑆 = 𝑛 𝐶𝑝 𝑑𝑇 + ℎ 𝑑𝑃
𝛿𝑄 = 𝑇𝑑𝑆 = 𝜆 𝑑𝑉 + 𝜇 𝑑𝑃

With S entropy, T temperature, P pressure and V volume

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 Thermodynamics
 Calorimetric Coefficients

 The isochoric heat capacity 𝐶𝑉 extensive quantity expressed in joule by kelvin ( J/K). It represents the heat absorbed by the
body at constant volume relative to the change in body temperature generated by this transformation, we have at constant
volume :

𝜕𝑆
𝐶𝑉 = T
𝜕𝑇 𝑉

And the formula of the variation of heat become 𝛿𝑄𝑉 = 𝑇𝑑𝑆 = 𝑛 𝐶𝑉 𝑑𝑇

 The isothermal expansion coefficient l, intensive quantity expressed in pascal Pa. It represents the heat absorbed by the body
at constant temperature relative to the change in body volume generated by this transformation, we have at constant
temperature:

𝜕𝑆
l=T
𝜕𝑉 𝑇

And the formula of the variation of heat become 𝛿𝑄𝑇 = 𝑇𝑑𝑆 = 𝑙 𝑑𝑉

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 Thermodynamics
 Calorimetric Coefficients

 The isobaric heat capacity 𝐶𝑃 extensive quantity expressed in joule by kelvin ( J/K). It represents the heat absorbed by the
body at constant pressure relative to the change in body temperature generated by this transformation, we have at constant
pressure :

𝜕𝑆
𝐶𝑃 = T
𝜕𝑇 𝑃

And the formula of the variation of heat become 𝛿𝑄𝑃 = 𝑇𝑑𝑆 = 𝑛 𝐶𝑃 𝑑𝑇

 The isothermal compression coefficient h extensive quantity expressed in cubic meter (m3). It represents the heat absorbed by
the body at constant temperature relative to the change in body pressure generated by this transformation, we have at constant
temperature :
𝜕𝑆
ℎ=T
𝜕𝑃 𝑇

And the formula of the variation of heat become 𝛿𝑄𝑇 = 𝑇𝑑𝑆 = ℎ 𝑑𝑃

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 Thermodynamics
 Calorimetric Coefficients

 A coefficient without a name attributed 𝜆 , intensive quantity expressed in pascal Pa. It represents the heat absorbed by the
body at constant pressure related to the variation of body volume generated by this transformation, we have at constant
pressure:

𝜕𝑆
λ=T
𝜕𝑉 𝑃

And the formula of the variation of heat become 𝛿𝑄𝑃 = 𝑇𝑑𝑆 = 𝜆 𝑑𝑉

 A coefficient without a name attributed 𝜇, an extensive quantity expressed in cubic meter (m3). . It represents the heat
absorbed by the body at constant volume related to the change in body pressure generated by this transformation, we have
at constant volume:

𝜕𝑆
𝜇=T
𝜕𝑃 𝑉

And the formula of the variation of heat become 𝛿𝑄𝑉 = 𝑇𝑑𝑆 = 𝜇 𝑑𝑃

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 Thermodynamics
 Thermoelastic Coefficients

The three thermoelastic coefficients are used to express the volume or pressure variation of a pure body or
a mixture with a constant composition during a reversible transformation:

Thermoelastic coefficients :
𝑑𝑉
= ─ 𝜒𝑇 𝑑𝑃 + 𝛼 𝑑𝑇
𝑉
1
𝑑𝑃 = ─ 𝑑𝑉 + 𝑃𝛽𝑑𝑇
𝑉 𝜒𝑇

With T( temperature), P(pressure), V (volume).

The isobaric expansion coefficient 𝛼 (intensive quantity expressed in K─ 1 ) is given by :

1 𝜕𝑉
𝛼=
𝑉 𝜕𝑇 P

The isochoric compression coefficient 𝛽 (intensive quantity expressed in K─ 1 ) is given by :

1 𝜕𝑃
𝛽=
𝑃 𝜕𝑇 V

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 Thermodynamics
 Thermoelastic Coefficients

The coefficient of isothermal compressibility (intensive quantity expressed in Pa─ 1 ) is given by :

1 𝜕𝑉
𝜒𝑇 = ─
𝑉 𝜕𝑃 T

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 Thermodynamics
Calorimetry
Calorimetry is a discipline of physics that concerns measurements of heat quantities.
 Massic Heat
The amount of heat that must be supplied at constant pressure to a body of mass m to raise its temperature
from 𝜃1℃ to 𝜃2℃ is given by this equation below:

Q  mc( 2  1 )
Où c is called the massic heat of the body under constant pressure (or specific heat).

In the international system of units, the unit of specific heat is joule per kilogram and per degree Celsius
(symbole :J.kg-1.°C-1) or joule per kilogram and Kelvin(symbole :J.kg-1.K-1).

 Heat Capacity
According to the previous relations, we can write that the heat Q can express :

Q  mc( 2  1 )   ( 2  1 )
The quantity µ is called calorific capacity of the expressed body J.°C-1 ou J.°K-1

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 Thermodynamics
Energy exchange
 During an elementary transformation, a system exchanges with the outside world a work 𝛿𝑊 and a quantity of heat 𝛿𝑄.
The internal energy of this system then undergoes a variation :
𝑑𝑈 = 𝛿𝑊+ 𝛿𝑄
 POSITIVELY the work and the heat RECEIVED by the system, and NEGATIVELY the work and the heat SUPPLIED by the system
in the middle outside.

Depend on states
of mattter
↓
U 2  U1  W1, 2  Q1, 2
↓
Independent on states
of matter

 Consider an open (non-cyclic) transformation passing the system from initial state 1 to final state 2, by several possible
paths 1A2, 1B2, 1C2. While the work 𝑊 A , 𝑊 B , 𝑊 C and heat quantities 𝑄A , 𝑄B , QC depend on the path followed.

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 Thermodynamics
Special cases
 In a cyclic transformation, the initial state 1 coincides with the final state 2 U1 =U2 , we have :
W  Q cycle  0
 In a isolated system (the system does not exchange anything with the outside environment), W = 0 and Q = 0,
we have then U1 =U2.
Expression of heat exchanged
In the general case, we have

Q  dU  W

For a reversible transformation :

Q  cv dT  ldv  c p dT  hdp  dv  dp

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 Thermodynamics
Specific cases
 During an isochoric process dv=0 :
Qv  cv dT
where Cv is the heat capacity at constant volume.

 During an isobaric process dp = 0.

Q p  c p dT

where Cp is the heat capacity at constant pressure.

 during an adiabatice process, Q  0

Variations of internal energy and enthalpy and their expressions

 Of the system receives only a work by pressure forces, then we have this relations below W   pdv

while
dU  Q  W  cv dT  (l  p )dv ; dH  d (U  pv)  Q  vdp  c p dT  (h  v)dp

dU et dH are truly and totaly differentials of internal energy and enthalpy.

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 Thermodynamics
Case of perfect gas
 A perfect gas obey at the first law of Joule : The internal energy is only a function of temperature, U = U(T)
U U
0 l p0
p v
Where we obtain l = p and :

dU  cv dT

It obeys also to the second law of Joule : Enthalpy is only a function of the temperature , H = H(T)

H H
0  hv 0
v p

Where we obtain h = ─v and :

dH  c p dT

Still in the case of a perfect gas 𝛾 1

𝜇= p and 𝜆= v
𝛾−1 𝛾−1

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 Thermodynamics
Heat Capacity

 We establish by considering the relation l = p Mayer law or relation of Mayer which relates heat capacity at
pressure and volume constant for n mol of perfect gas,
c p c v  nR

By including the ration

cp

cv
The Mayer relation is written by this following equation :

cv (  1)  nR
Then we obtain :
cv 
nR nR
cp 
 1  1
Case of perfect gas:
For a reversible adiabatic process of a perfect gas we have these relations below :
𝑃 𝑉 𝛾 = 𝐶𝑡𝑒 𝑇 𝑉 𝛾−1 = 𝐶𝑡𝑒 𝑇 𝑃 1−𝛾 𝛾 = 𝐶𝑡𝑒

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