Chapter 6: Thermodynamics

Prof. Felice Iazzi Dipartimento di Fisica del Politecnico di Torino
e-mail : felice.iazzi@polito.it tel. 3355995361

$=1: Temperature
Temperature Temperature is a common feeling: it becomes a quantity when is defined through an instrument, which measures it. To measure the temperature we profite of the volume dilatation that occurs practically in all bodies when they are heated: we define 0 unit the temperature of a mixing of water and ice and 100 units the temperature of the boiling water. The unit is called degree “centigrade”, its symbol is C. If we take a body (for instance a thin long rod of copper) and we measure its volume () putting it in contact with a mixing of water and ice (let’s call it V(0) ) and the same with boiling water (let’s call it V(100) ), the temperature Θ [C] will correspond to a dilated volume
V (Θ) =V (0) + Θ ∗( V (1 0 −V (0 0) )) 100

(6.1.1) This procedure is an example of measurement of the temperature and the instrument (in this case, the rod) is called thermometer: using (1), from the measurement of the volume of the thermometer one gets the temperature Θ . Remark: for volumes smaller than V(0) the temperature reads negative! To define the temperature and the measurement procedure we assumed the following law, called “0th - law of thermodynamics”: When n bodies are put in contact, after enough time they will reach the same temperature (this situation is called thermal equilibrium). Temperature scales Also the gases increase their volumes when heated. In particular, let’s rewrite the Gay-Lussac law for ideal gases:

∆V = const ⋅ ∆Θ

(at

constant pressure)

(6.1.2)

as:

V (Θ) −V (0) = const ⋅ (Θ − 0) ⇒V (Θ) = V (0) + const ⋅ (Θ − 0) = V (0)(1 +α ⋅ Θ) (6.1.3)

The value of α = 1/(273.15 +-0.01) (C-1) is the same for all ideal gases and from (6.1.3) we deduce that temperature has a minimum at Θ min =−273.15 (C). A scale using the same unit (degree centigrade) but the 0 value at Θ min is preferred in thermodynamics: it is called absolute scale or Kelvin scale. Coming back to the 0th - law of thermodynamics, it has been observed that the final temperature follows the law:

∑ m c (Θ
i =1 i i

n

i

−Θf ) = 0

(6.1.4)

where mi and Θ i are mass and initial temperature of the i-th body and ci is a constant depending on the material of the i-th body. The constant ci is called “specific heat” and mi ci is called thermal (or heat) capacity. From (6.1.4), Θ f is given by the following relationship:

Θf =
(6.1.5)

∑m c Θ
i =1 n i i

n

i

∑m c
i =1

i i

The above observed phenomenon has been described in the following way: When a body changes its temperature of ∆ Θ , a quantity called heat flows from outside into the body (if ∆ Θ >0) or from the body to outside (if ∆ Θ <0). The value ∆ H of the transferred heat is given by:
∆H = m ⋅ c ⋅ ∆ Θ

(6.1.6)

The unit of heat is called kilo-calory or kilo-calorie (kcal) defined as the amount of heat necessary to lead 1 kg of pure water (at 1 atm pressure) from 14.5 C to 15.5 C. Another unit often used is the calory (cal) defined by: 1 kcal = 1000 cal. Changes of state Sometimes, bodies change their state: from solid to liquid (melt) and inversely from liquid to solid (solidification); from liquid to gas (evaporation or boiling) and inversely from gas to liquid (liquefaction). During a change of state a body maintains constant its temperature (called melting or solidification or evaporation or liquefaction temperature) until the whole mass changed the state. During this time an amount Ql of heat is transferred to (melting and evaporation) or taken

away from (solidification and liquefaction) the body. This amount is related to the body mass m by the relation: Ql = mλ , whereλ is a (nearly) constant parameter called “latent heat” for the specific process and depends on the body’s material and, of course, on the process.

$=2: Exercises about calorimetry
Exercise 6.2.1 In a vessel containing a mass m of water at temperature ϑ, another mass m at 1 1 2 temperature ϑ is added. After a long time the final temperature of the whole water is 2 but the transformation is not adiabatic. How much heat has been released to the vessel? DATA: m =1.5 [kg]; m =2.5 [kg]; ϑ=50 [kg]; ]; ϑ =15 [C]; ϑ=20 [C]; f 1 2 1 2 Solution: ; ; ; Exercise 6.2.2 A mass of Cu at temperature is put in contact with, mass of ice at temperature . Find the mass m of ice which will be transformed into water after a long time, and the final temperature , of the system water + Ice if the transformation is adiabatic. DATA: ; ; Solution: ; ; Is necessary to to go to Is necessary to ice to go to C remains available to melting process when both ice and Cu are at ; ;

ϑ f

temperature.

Exercise 6.2.3 In an insulated container 2 kg of water at 20 C are contained: a Cu body at 70C and 1 kg of ice at – 10C are put inside the water. Which final temperature will be reached after long time and how much ice will survive at that time?

General Solution Let solve the following more general problem: if n bodies of mass, specific heat and temperature (mi, ci, Θ i) and 2 bodies of the same matter but different state (like ice and water, water and vapour…), with mass, specific heat and temperature (MA, cA, Θ A , MB, cB, Θ B) are put all together in an insulated container, what will be the final situation in terms of temperature and masses? Let’s suppose that the temperature of the change of state for A and B is Θ c and that for all the other bodies are outside the range of Θ i. Let’s also suppose that the change of state from A to B requires heat and λ be the corresponding latent heat. Solution: The 0-th law states that after enough time the temperature will be uniform, doesn’t matter which way. Therefore we are free to imagine every temporary exchange of heat among all bodies before they reach the equilibrium. Let’s imagine the following steps: Step 1: all bodies reach the temperature Θ c; the total heat Qexcess absorbed or emitted by the bodies is defined as: Qexcess ≡ ∑ mi ci (Θ i − Θ c )
i =1 n

Step 2: if Qexcess is positive means that at Θ c some heat remains available to make a change of state A B, on the contrary if Qexcess is negative some heat is needed to make a change of state B A:
Qexcess > 0 ⇒ A → B Qexcess < 0 ⇒ B → A

Let be, for example, A B: Step 3: let’s calculate the total heat QAB = MA λ , required for changing all MA into the state B and compare it with Qexcess: a) If: Qexcess < QAB : the final temperature will be Θ c and MAB = Qexcess /λ will be the part of MA which will change the state from A to B; b) If: Qexcess > QAB : all MA changes state spending QAB : the remaining heat Qr = Qexcess- QAB will be available to enhance the temperature from Θ c to Θ f without further changes of state. The final temperature Θ f will be found using Eq.(6) with Θ i = Θ c and cB holding for the total mass MA + MB. Q r = ∑ [ mi c i + ( M A + M B )c B ] (Θ f − Θ c )
i =1 n

If B A is the case, the procedure will be analogous from Step 3 (a and b) with B emitting heat until all or a part will reach the state A. Exercise N. 6.2.4

A cube of iron of mass m1 and temperature θ 1 is put over another cube of lead of mass m2 and temperature θ 1 , which in turn is put is put over another cube of silver of mass m3 and temperature θ 3. All the system is in a vacuum chamber (a totally empty container) whose floor is adiabatic, i.e. doesn’t allow the heat to flow through (therefore the system is completely insulated). Find the final temperature at the equilibrium. Data: m1= 0.2 [Kg] ; m2= 0.5 [Kg] ; m3= 1.2 [Kg] ; θ 1= 20 C; θ 2= 200 C; θ 3= 120 C (Sol.: θ f=110.253) Exercise N.6.2.5 A cube of ice of mass m1 and temperature θ 1 is put inside a cup of water. The mass of the water is m2, its temperature is θ 2 and the cup is adiabatic. Find the final temperature at the equilibrium. Data: m1= 0.4 [Kg] ; m2= 2.5 [Kg] ; θ 1= -20 C; θ 2= 60 C Exercise N. 6.2.6 A mass m1 of ice at temperature θ 1 is put inside a cup of water. The mass of the water is m2, its temperature is θ 2 and the cup is adiabatic. Find the final temperature at the equilibrium. Data: m1= 0.4 [Kg] ; m2= 1.5 [Kg] ; θ 1= -20 C; θ 2= 20 C Exercise N. 6.2.7 In the exercise 6.2.6 suppose that the cup is made of aluminium and has a mass m3. Find the final temperature at the equilibrium. Data: m1= 0.4 [Kg] ; m2= 1.5 [Kg] ; m3= 0.3 [Kg] ; θ 1= -20 C; θ 2= 20 C Exercise N. 6.2.8 In the Exercise N. 6.2.4 the floor is not adiabatic and when the masses reach the thermodynamic equilibrium an amount H of heat flowed away. Find the temperature at this time.

$=3: Heat transfer
Heat flows from the points at higher temperature to the adjacent points at lower temperature in the space. There are 3 kinds of heat transfer: internal transfer, external transfer and radiation. Internal transfer Let’s consider a thin layer of infinitesimal thickness dx and large finite surface S, perpendicular to the x axis: let’s suppose that the temperature is the same on all the surface passing through x. (x) On both sides of the layer the temperature is Θ and Θ(x+dx) =Θ(x) +dΘ respectively. In the time interval dt an amount dQ of heat flows from side x to side x+dx, which is proportional to the surface S, to dt , to dΘ and inversely proportional to dx:

dQ = −kS

dΘ dt ⇒ dx

dQ dΘ =−kS dt dx

(Fourier law)

(6.3.1)

where: k = internal heat transfer coefficient S = surface through which heat flows dx = thickness of the body through which heat flows External transfer Let’s consider a body at temperature Θ , whose surface S is surrounded by a gas at B Θ : heat flows from the body to the gas (or viceversa) obeying the following temperature G law:
dQ = h⋅S ⋅∆ Θ dt

(Newton law)

(6.3.2)

where: h = external heat transfer coefficient (or Newton coefficient) ∆Θ ≡ ΘB −ΘG = Temperature difference between the body and the far fluid S = surface which heat flows through Radiation Each body emits electromagnetic waves which bear energy: since heat is energy, as we shall see in the following, the emission causes a loss of heat of the body and
W = σ ⋅T 4

(Stefan law)

(6.3.3)

Where: W is the heat emitted per unit time and unit surface. −2 σ = Stefan constant ( σ ≈ 5.67 ⋅10 −8 [W⋅ m ⋅ K −4 ] for black body) T = body temperature Exercise N. 6.3.1 An iron heater contains hot water, which flows through, at constant temperature θ in. The heater is inside a big room whose temperature θ out is constant. The shape of the heater is nearly a parallelepiped of total surface S and the thickness of the iron is d. Find the amount ∆ H of heat lost by the water in 1 hour, under the hypothesis of heat transfer at equilibrium. Data: θ in= 60 C; θ out= 21 C; S = 10 m2; d = 3 mm Solution: As a reference system let us assume an x axis perpendicular to the large surface of the parallelepiped, with positive direction from the internal water (where temperature is θ in) to the external water (where temperature is θ out). Recalling that the “at equilibrium” hypothesis requires:

dH dθ = 0 ⇒ H = H (t ); = 0 ⇒ θ = θ ( x) , and that θ (x) is a continuous function, we can dx dt

write:
θ out θ in

∫ dθ = θ

out

− θ in

and solve the Eq.(4.3.1) of the internal heat transfer (Fourier law):
dH dθ dθ 1 dH = −kS ⇒ =− ⇒ θ out − θ in = dt dx dx kS dt =−
x =d

θ out θ in

∫ dθ = ∫
0

d

dθ dx = dx

x =d

x =0

∫ − kS

1 dH dx = dt

1 dH d dH dH kS kS ⋅ ∫ dx = − ⇒ = ⋅ (θ in − θ out ) ⇒ ∆H = ⋅ (θ in − θ out ) ⋅ 3600[ s ] kS dt x =0 kS dt dt d d

Exercise N. 6.3.2 The same heater of the Exercise N. 6.3.2 is completely dipped in an adiabatic basin containing a mass m of hot water initially at temperature θ 0. The internal water, which flows inside the heater, is maintained always at the same temperature θ in. The water outside receives heat continuously from the heater and this heat is quickly diffused through all the water in such a way that the temperature is always uniform. Find the temperature of the outside water after a time ∆ t. Data: θ in= 80 C; θ 0= 10 C; S = 10 m2; d = 3 mm; ∆ t = 40 [s]; m = 200 [kg] Solution: As in Exercise N. 6.3.1 the heat, which flows from the inside to the outside water obeys to the Fourier law, but in this case the destination temperature increases during the time because the external water is inside an adiabatic basin which saves the heat. Therefore the external water is a system obeying to the calorimetric law:
dH = dH dt = m ⋅ c ⋅ dθ , dt

where c is the specific heat of the water. Taking into account that the external water temperature θ = θ(t ) is a function of the time. Going ahead in the solution of the Fourier equation: θ (t ) d x =d 1 dH 1 dH dH kS θ (t ) − θ 0 = ∫ dθ = ∫ − dx = − ⋅ ∫ dx ⇒ = ⋅ (θ in − θ (t )) kS dt kS dt x =0 dt d θ 0
in

Using also the equation of calorimetry we get the system:

dH kS  d t = d ⋅ (θ i n − θ (t ) )   d H= d Hd t= m ⋅ c ⋅ dθ  dt

, whose solution in θ (t) is:

θ (t ) = θ in + (θ 0 − θ in ) ⋅ e

kS t d ⋅m⋅c

Exercise N. 6.3.3 A room of a flat has 2 walls in contact with the outside air, which is at constant temperature θout . Inside the room there is a heater, which produces a constant rate of heat room temperature at θ . All the other walls, the floor and the ceiling are in contact with other in rooms at the same temperature θ . Both walls in contact with outside are made by 2 adjacent in layers: one of concrete toward inside and one of fibre toward outside: thickness of concrete is d and thickness of fiber is d2 . The total surface of the walls is S. Find the heat produced 1 by the heater in half an hour, under the hypothesis of stationary flow of heat.
2 ] ] DATA: θout =−1[C]; θin = 20[C] ; d1 = 20[cm ; d2 = 4[cm ; S = 30[m ]

dQ , maintaining the dt

Solution: First let’s assume that the 2 walls, which make an angle of 90° to each other, are equivalent to only one total planar surface S. This approximation is more valid as bigger is S. As a reference system let us assume an x axis perpendicular to the total equivalent surface of the walls, with positive direction from the internal air (where temperature is θ in) to the external air (where temperature is θ out). Recalling that the “stationary” hypothesis requires:
dH dθ = 0 ⇒ H = H (t ); = 0 ⇒ θ = θ ( x) , dx dt

we can write the Fourier law for each slab, defining θ the temperature on the contact s surface between both surfaces:
S dH dθ dθ 1 dH = −k1S ⇒ =− ⇒ θ S − θin = ∫ dθ = dt dx dx k1S dt θin

θ

x=d1 x=0

dθ dx = dx

in the concrete:

=

x=d1 x=0

1 1 dH 1 dH d dH dx = − ⋅ ∫ dx = − 1 ⇒ k1S dt k1S dt x=0 k1S dt

x=d

dH k1S = ⋅ (θin − θ S ) dt d1

in the fibre: θout x=d1+d2 dH dθ dθ 1 dH dθ = −k2 S ⇒ =− ⇒ θout − θ S = ∫ dθ = ∫ dx = dt dx dx k2 S dt θS x=d1 dx

=

x=d1 +d2 x=d1

1 dH 1 dH − dx = − ⋅ k2 S dt k2 S dt

x=d1+d2 x=d1

dx = −

d2 dH ⇒ k2 S dt

dH k2 S = ⋅ (θS − θout ) dt d2 The heat rate is the same in both concrete and fibre and is due to the stationary condition ⇒

Thermodynamic parameters of some materials
Internal Melting Melting Boiling Boiling conductivity temperature latent heat temperature latent heat coeff. cal/(K s C Kcal/kg C Kcal/kg cm) 669 94.9 2520 2604 0.566 1.03 0.19

Material Unit Steel Aluminum Silver Calcium Iron Nickel Gold Lead Platinum Copper Glass Aceton Water Ethilic alcool Metilic alcool Benzol Clorophormium Mercury Olive oil Oil Toluol Xilol Hydrogen Helium Oxigen Tin Ice Marble Air

Specific Heat Kcal/(kg K) 0.144 0.217 0.057 0.170 0.114 0.108 0.032 0.031 0.031 0.093 0.190 0.528 0.998 0.581 0.600 0.406 0.226 0.033 0.474 0.498 0.403 0.397

1538

65

2862

1620

0.084 1085 49.5 2563 1760 0.96 (1 - 3) .10-3 1.43 .10-3

0

79.7

100

539.8

-39

2.7

357

70.04

0.02

-259 -219 232 0

14.3 3.3 14.5 79.7

0.5

-253 -269 -183 2603 100

107.6 4.78 50.8 650 7.5 .10-3 5.3 .10-4 5.6 .10-5

$=4:Thermodynamic transformations
Thermodynamic systems can be described by macroscopic quantities: in general, pressure P, volume V and temperature T are used. Remarks: sometimes the temperature inside a body is not uniform, i.e. temperature of the body is not defined. The same occurs sometimes for gases. When all these macroscopic quantities are defined for a system, i.e. each one assumes a value at a certain time, it is said that the system is in the state (P,V,T). Equation of state: for all systems P,V and T are not independent but are related to each other by an equation, called “equation of state”. A typical example is the equation of state of the ideal gases:
P ⋅V = n ⋅ R ⋅ T

(6.4.1)

where n is the mole number of the gas and R = 8.314 [J/K.mole] = 0.08205 [litre.atm /K.mole]. When a system is in the following conditions: 1) each part of the system is submitted to a total external mechanical force equal to 0 2) each part of the system doesn’t transform chemically 3) each part of the system has the same temperature the system is said to be in “thermodynamic equilibrium”. Transformations When a system changes the values of (P,V,T) we say that it undergoes to a thermodynamic transformation. A “finite” thermodynamic transformation from the state (P0,V0,T0) to the state (P1,V1,T1 ) proceeds through infinitesimal changes (dP,dV,dT) of the thermodynamic quantities. If the initial and final states are the same the transformation is called “cyclic transformation”. Reversibility of the thermodynamic transformations When a thermodynamic transformation proceeds through consecutive infinitesimal transformations, each one leading to an equilibrium state, the transformation is called “reversible”. When this requirement is not fulfilled, the transformation is called “irreversible”. In general to be reversible, a thermodynamic transformation requires to be very slow: “slow transformation” is usually assumed as synonymous of reversible. Special transformations
1)

Adiabatic transformation: the thermodynamic system does not receive nor gives any heat

Isothermal transformation: the thermodynamic system maintains its temperature constant during the transformation 3) Isobaric transformation: the thermodynamic system maintains its pressure constant during the transformation 4) “isovolumic” transformation: the thermodynamic system maintains its volume constant during the transformation
2)

Work of a system When a system changes its volume, its surface varies: the surface is submitted to pressure from inside and from outside and the internal and external pressure can be nearly equal (reversible transformation) or different (irreversible transformation). The work made by the system on the outside world is given by:
dW = P ⋅ dV

(6.4.2)

where P is the external pressure and the sign of dW is taken positive if the work is made by the system against outside (expansion of the thermodynamic system) and negative if made by outside on the system (shrinking of the thermodynamic system). For a thermodynamic system described by the quantities (P,V,T) the transformations can be represented as curves in the (P,V) plane or in the (P,T) plane or in (V,T) plane, due to the fact that in each pair the third variable can be obtained from the state equation. Conversion of units: 1 litre-atm = 101.3 J; 1 atm = 1.01325 105 N/m2 = 1.01325 105 Pa Exercises on the thermodynamic transformations 1) A volume V0 = 22.4 litre of an ideal gas at pressure P0= 1 atm is heated very slowly and it transforms following the law:
P = P0V02 /V 2

Find pressure and temperature when volume becomes twice the initial one and the work done by the thermodynamic system. 2) A volume V0 = 2 litre containing 0.5 mole of an ideal gas at pressure P0= 1 atm is heated very slowly and it transforms following the law: Find pressure and temperature when temperature becomes twice the initial one and the work done by the thermodynamic system. 3) A volume VA contains n mole of a bi-atomic ideal gas, initially at temperature TA. Burning an amount M of methane, whose calorific power P (produced heat per unit mass) is 13271 [kcal/kg], the temperature is slowly doubled, simultaneously expanding the volume in order to maintain constant the ratio
T2 . Assuming that no heat is wasted in the environment, find: V

P ⋅ T = const

The initial and final values of the pressure The work W produced by the gas The value of M DATA: n= 0.3 [mole]; R= 0.082 [litre*atm/(mole*K)] ; VA=9 [litre] ; TA=300 [K]; 1 [cal]=4.18[J]]
1) 2) 3)

Solution Exercise 3
p A = 0.82

1) V A = 9
T A = 300

1 p A ≈ 0.41 2 V B = 36 pB = TB = 2T A = 600

2) W AB = 2nRT A
U AB = nCV (TB −TA ) = 5 R⋅TA ≈ 0.09945[Kcal] 2

3) H AB =U AB +W = AB
M=

9 R⋅TA ≈ 0.17901[Kcal] 2

H AB ≈1.34888E-05[Kg] P

$=5: Ideal gas
An ideal gas satisfies the equation of state (4.4.1) when is in equilibrium. Work of some typical transformations of an ideal gas 1) Isovolumic transformation from (VA,PA,TA) to (VA,PB,TB):
W AB = ∫ dW = ∫ P ⋅ dV = 0
A A B B

(6.5.1)

Remarks: in an isovolumic transformation the work of an ideal gas is 0. It’s easy to see that this result holds for all thermodynamic systems. 2) Isobaric transformation from (VA,PA,TA) to (VB,PA,TB):
W AB = ∫ dW = ∫ P ⋅ dV = P ⋅ ∫ dV = P ⋅ (V B − V A )
A A A B B B

(6.5.2)

Remarks: in an isobaric reversible transformation the work is given by P.∆ V. It’s easy to se that this result holds for all thermodynamic systems

3) Isothermal reversible transformation from (VA,PA,T) to (VB,PB,T): B B B B V nRT dV W AB = ∫ dW = ∫ P ⋅ dV = P ⋅ ∫ dV = nRT ∫ = nRT ⋅ ln( B ) V V VA A A A A (6.5.3) Remark: we profited of the reversibility property using the equation of state, which holds only for equilibrium gases.

$=6: The I law of Thermodynamics
The definition of the quantity “work of thermodynamic systems” allows finding a relationship between the mechanics and the thermodynamic quantity “temperature”, through pressure and volume. Also heat can be related to the work and this relationship is called the “I Law of Thermodynamics”. It is a principle, i.e. a result of several experimental observations, never contradicted up to now. This principle leads to the discovery of a new quantity, the internal energy, whose properties play a role in thermodynamics equivalent to that of the potential in mechanics. To make an example of the kind of observations leading to the principle we start studying 2 transformations of n mole of a gas, both starting from an equilibrium point A and arriving to an equilibrium point C (Fig. 6.6.1.a). The goal is to evaluate the total heat exchanged by the gas with the surrounding environment. In other words we solve the following problem: “ n mole of an ideal gas is contained in a cylinder, with a moving piston, at initial volume, pressure and temperature VA, pA, TA (Fig. 6.6.1.b). The piston and the lateral wall of the cylinder are insulators, while the thin basis (of small thickness d) is separated, by a sliding insulator septum, from a thermostatic source at temperature TS >TA . Connecting gas and source, some heat passes to the gas, inserting the septum the gas is totally insulated. The gas undergoes an isothermal transformation with volume expansion to V , followed by B an isovolumic transformation to the temperature TC <TA . Both transformations are reversible. The work from A to C through B is given by eqs. 6.5.1 and 6.5.3:

VB ) (6.6.1) VA If the gas goes from A to C first along an isovolumic down to D at temperature T and then to C C along an isothermal DC, the work is different: V WADC = nRTC ⋅ ln( B ) (6.6.2) VA Let’s now try to evaluate the heat exchanged by the gas with the outside environment along the 2 different paths ABC and ADC. “ Along the 2 isovolumic transformations the heat flows from the gas to outside and is the same from A to D and from B to C: ∆H AD = ∆H BC = n⋅C V ⋅(TC −TA ) where C V is the specific heat at constant volume. It must be remarked that in the isovolumic transformation the exchanged heat transforms only into temperature. W = nRTA ⋅ ln( ABC

In order to evaluate the exchanged heat along the isothermal TA we can suppose to follow an infinitesimal isobaric transformation from VA to VA +dV , followed by an infinitesimal isovolumic transformation from pA to pA − dp, such that pA − dplies again on the isothermal. Let’ suppose to make the former transformation leaving the basis in contact with the source for an infinitesimal time dt , during which the system moves infinitesimally far from the equilibrium state and the latter inserting the septum for enough time to allow the gas to reach a new equilibrium state in the same temperature TA with infinitesimally smaller pressure. The heat is exchanged only during the isovolumic transformation because, during the isobaric one, the gas is insulated. The exchanged heat can be evaluated in this way: from the point (VA, pA, TA ) to (VA + dV, pA, TA + dT) the system is close to the equilibrium state and we can write:

(VA + dV)⋅ pA ≅ nR(TA + dT) → pA VA + dV ⋅ pA ≅ nRTA + nRdT → dT =
dH = dt⋅ kS kS dT = dt⋅ ⋅ dV ⋅ pA d d⋅ nR

and using the Fourier Law (steady state condition are fulfilled in an infinitesimal time interval): (6.6.4)

pAdV nR

(6.6.3)

From eq. 6.6.4 we see that in the first infinitesimal step of the isothermal TA the exchanged heat in the expansion dV is proportional to the pressure pA : in the analogous expansion dV from the point D along the isothermal T , the exchanged heat is proportional to p through C C TA . Further analogous the same proportionality factors, therefore it is less than in infinitesimal steps can be followed from (VA + dV, pA, TA + dT) to (VA + 2 ⋅ dV, pA,TA + 2 ⋅ dT) and so on, up to B and similarly along T . In each pair on TA C T (corresponding to the same volume change dV ) the exchanged heat is greater along and C TA than T . Remembering that along AD and BC the exchanged heat is equal, we can C conclude that in the total transformation fro A to C the exchanged heat depends on the path followed by the gas.

Fig. 6.6.1.a

Fig. 6.6.1.b

, Remark: from the point (VA +dV, pA,TA + dT) to the point (VA +dV, pA − dp TA ) (isovolumic) an amount of heat equal to (dH = −n⋅CV ⋅ dT) “disappears” and no work is done: we shall see that such heat is not destroyed but transformed into another quantity called internal energy.
The statement of the I Law of Thermodynamics In the previous example we found that both the produced work and the exchanged heat during a transformation depend on the path followed on the plane (p,V). Therefore the initial and final points of the transformation are not sufficient to evaluate these 2 quantities. To represent such a feature, the infinitesimal work and heat of each infinitesimal step are written as δW, δH instead of using the differential form dW, dH : this symbol means that the integral of δW, δH from A to B needs the knowledge of the path γ. Several measurements were done in the past of exchanged heat and produced work in different transformations of various thermodynamic systems and always it has been found that the difference between both quantities in the transformations having the same initial and final points was the same, independently on the transformation. This result assumed as a law, can be expressed in infinitesimal terms as:

δ H − δW = dU

(I Law of Thermodynamics)

(6.6.5)

where U is the function “difference of heat and work” and is written as usual differential because its integral doesn’t depend on the transformation. This quantity U is called “Internal Energy”. Remarks about I Law Looking at eq. (6.6.5) we can imaging: 1) adiabatic transformations: δH = 0, →δW = −dU 2) isovolumic transformations: δW = 0, → δH = dU 3) transformations with same initial and final point A:
A,γ

∫ δH −

A

A,γ

∫ δW =

A

∫ dU =U(A) −U(A) = 0
A

A

We see that both heat and work can transform into internal energy: when no heat is exchanged, the produced work decreases the internal energy of the system (and viceversa), when no work is produced, the heat going into the system increases the internal energy (and viceversa). Moreover, in the transformations having closed path, heat and work transform into each other. We can conclude that heat, work and internal energy are quantities with the same dimensions. Therefore the units for heat and work are equivalent and the conversion factors are given as: Units: 1 Kcal = 4184 J = 1000/0.239 J

$=7: The I Law of Thermodynamics and the ideal gas

The Joule experiment and the internal energy for an ideal gas One can expect that the internal energy U of an ideal gas is in general an explicit function of p,V,T, (among which only 2 are independent and the 3-th is deduced from the equation of state):
U =U (V , p, T ) (6.7.1) From the Analysis we know that the infinitesimal variation of U is given by:

dU =

∂U (V , p, T ) ∂U (V , p, T ) ∂U (V , p, T ) dV + dp + dT ∂V ∂p ∂T

(6.7.2)

Joule experiment was made in this way: 2 identical spheres were connected by a pipe and a septum inside the pipe separated 2 identical volumes. The rigid walls of the spheres and the pipe were adiabatic and 2 thermometers were inserted in the 2 volumes in order to monitor continuously the temperature. An amount of n mole of gas (at low pressure) were contained in one sphere, while the other one was empty. The septum was suddenly opened away in order to allow the gas to expand in the empty sphere. The new temperature of the gas was found to be the same in both volumes and equal to the initial one of the gas. Discussion of the result of the Joule experiment Taking into account that the walls were adiabatic, gas didn’t exchange any heat with the external world: δH = 0 . Also the work made by the gas on the external world was 0, because the walls were rigid and therefore no displacement was done. From the I thermodynamic law we deduce: 0 = dU =
∂U (V , p, T ) ∂U (V , p, T ) ∂U (V , p, T ) dV + dp + dT ∂V ∂p ∂T

(6.7.3) We know from the experiment that in the last formula the temperature is constant, i.e. dT = 0 . The other terms must be 0 in order to satisfy the equation but the differentials are not 0 because both volume and pressure change. Therefore each partial derivative with respect V and p must be 0, i.e. the internal energy doesn’t depend on them, but only on the temperature (whose partial derivative can be different from zero because its term is zero due to the differential):
U =U (T )

Remark about the internal energy, heat and friction work in solid and liquid bodies Let’s consider a system made by 2 rigid bodies in contact and insulated, e.g. a cube A sliding on the rough surface of a second cube B. An initial kinetic energy Ec is given to A. The kinetic energy is dissipated by the friction work W = Ec until A stops. The system underwent an adiabatic transformation and the work W is totally transformed into internal energy of the 2 cubes. It is common experience that the temperature of A and B increases, therefore the friction work transformed into heat inside the bodies. This phenomenon shows that the energy dissipated by the non conservative mechanical forces is transformed into heat and the conservation of the mechanical energy is extended to the dissipative forces by including the heat among the different forms of the energy. An analogous experiment can be done dissipating energy into viscous work inside a liquid.

Specific heat for ideal gas From observation it has been stated that the specific heat of an ideal gas is different for different types of transformations. In particular the specific heat at constant volume is different from the specific heat at constant pressure. Moreover, for measuring the amount of a gas, it’s easier to use the number of moles instead of the mass. Therefore in the following we speak of specific heat per unit mole and not per unit mass. It must be recalled that the equation of state of one mole of ideal gas simply reads: PV = RT. Mayer relationship for specific heat Let’s calculate the specific heat of an ideal gas at constant volume (CV) starting from the definition (4.1.6) written for an infinitesimal amount of transferred heat to 1 mole of gas:
δH = CV ⋅ dΘ

(6.7.4) Where the symbol δ has been used to recall that the amount of exchanged heat depends on the specific transformation. Using the I law and remembering that dV = 0 , we get:
CV =

(6.7.5)

δH pdV + dU dU = = dΘ dΘ dΘ

With the same procedure we can now calculate the specific heat of an ideal gas at constant pressure (CP) remembering that from the equation of state, when T = const, one has pdV = Rd Θ:
Cp =

δH

=

From this formula we can get the Mayer theorem: C p = CV + R Work, heat and internal energy in special transformations of an ideal gas Let’s suppose that 1 mole of gas initially in the state A (VA, pA, TA) undergoes a transformation to the state B (VB, pB, TB). We go to calculate the work WA,B, the heat transfer HA,B and the variation of internal energy U(B)-U(A) of the gas for a) an isovolumic transformation, b) an isobaric transformation, c) an isothermal reversible transformation, d) an adiabatic reversible transformation. Isovolumic transformation Remembering that in an isovolumic transformation dV = 0 , using the I law:
δH = pdV + dU = CV ⋅ dΘ

pdV + dU pdV dU RdΘ = + = +CV dΘ dΘ dΘ dΘ

(6.7.6)

(6.7.7)

we get:

W A, B = ∫ pdV = 0
A

B

U ( B ) − U ( A) = ∫ dU = ∫ CV dΘ = CV [ Θ( A) − Θ( B )]
A A

B

B

(6.7.8)

H A, B = ∫ δH = ∫ dU = CV [T A − TB ]
A A

B

B

Isobaric transformation ( p=const)
W A, B = ∫ pdV = p A ⋅ ∫ dV = p A ⋅ [V B −V B ]
A A B B

U ( B ) −U ( A) = ∫ dU = ∫ CV dΘ = CV [T A − T B ]
A A

B

B

(6.7.9)

H A, B = ∫ δH = ∫ pdV +∫ dU = p A ⋅ [V B −V B ] + CV [T A − T B ]
A A A

B

B

B

Isothermal reversible transformation ( T = const ⇒ dT = 0 ) B B B RT A V dV W A, B = ∫ pdV = ∫ dV = RT A ⋅ ∫ = RT A ⋅ ln B V V VA A A A
U ( B ) − U ( A) = ∫ dU = ∫ CV dΘ = 0
A A B B

(6.7.10)
VB VA

H A, B = ∫ δH = ∫ pdV +∫ dU = ∫ pdV = RT A ⋅ ln
A A A A

B

B

B

B

Adiabatic reversible transformation ( δH = 0 ) Before calculating WA,B, HA,B and U(B)-U(A), we can deduce the equation of an adiabatic curve, using the I law. Let’s define γ ≡
Cp CV

. (6.7.11)

δH = 0 = pdV + dU ⇒ pdV = −dU = −CV dT

Using the equation of state, we can write Eq. (4.7.11) as: C dT C dT RT dV dV dV = −CV dT ⇒ =− V ⇒∫ = ∫− V ⇒ V V R T V R T C C ⇒ ln(V ) = − V ln(T ) + ln(const ) ⇒ ln(V ) + V ln(T ) = ln( const ) ⇒ R R
⇒ VT
CV R

(6.7.12)

= const ⇒ V

R CV

T = const

R CV

Using the Mayer theorem:
Cp

V CV T = TV γ −1 = const
And using the equation of state we get:
pV
γ

−1

(6.7.13)

= const

(6.7.14) Now we can go on to calculate WA,B, HA,B and U(B)-U(A):
B B

W A, B = ∫ pdV = −∫ dU = −CV [T A − TB ]
A A

U ( B ) − U ( A) = ∫ dU = ∫ CV dΘ = CV [T A − TB ]
A A

B

B

(6.7.15)

H A, B = ∫ δH = 0
A

B

Carnot cycle In the plane of coordinate (V,p) the starting point of the cycle is A (VA,pA,TA), expands to B(VB,pB,TB=TA), through an isothermal transformation, still expands to C(VC,pC,TC), through an adiabatic transformation, then the volume shrinks to D(VD,pD,TD=TC), through an isothermal transformation, still shrinks to A(VA,pA,TA), through an adiabatic transformation. Let’s now calculate the work, the heat transfer and the variation of internal energy of the ideal gas in each transformation AB, BC, CD, DA. Isothermal transformation AB
W A, B = RT A ⋅ ln VB VA

U ( B ) −U ( A) = 0 H A, B V = RT A ⋅ ln B VA
C

(6.7.16)

Adiabatic transformation BC
W B ,C = ∫ pdV = −∫ dU = −CV [TC − T A ]
B B C

U (C ) − U ( B ) = ∫ dU = ∫ CV dT = CV [TC − T A ]
B B

C

C

(6.7.17)

H B ,C = ∫ δH = 0
B

C

Isothermal transformation CD
WC , D = RT C ⋅ ln V VD = −RT C ⋅ ln C VC VD

U ( D ) − U (C ) = 0 H C , D = RT C ⋅ ln V VD = −RT C ⋅ ln C VC VD
A

(6.7.18)

Adiabatic transformation DA
W D , A = ∫ pdV = −∫ dU = −CV [T A − TC ]
D D A

U ( A) − U ( D) = ∫ dU = ∫ CV dT = CV [T A − TC ]
D D

A

A

(6.7.19)

H D , A = ∫ δH = 0
D

A

Using the equation (6.7.13) for BC and DA adiabatic transformations, we get: γ −1 γ −1 T AV B = TC VC V V ⇒ B = C γ −1 γ −1 V A VD T V =T V
C D A A

(6.7.20)

Using (6.7.20) , from (6.7.16) and (6.7.18) we see that work and exchanged heat are equal in modulus and opposite in the isothermal transformations. If the amount of gas in the Carnot machine is n mole instead of 1, all the previous results remain valid making the substitutions: R → nR ; CV → nC V Efficiency Definition: the efficiency of a cyclic machine is the ratio of the total work made by the machine in one cycle to the amount of absorbed heat. Remark: the efficiency takes into account the sum of all the works (positive and negative) made during each branch of a transformation, but takes into account only the absorbed heat. As an example let’s calculate the efficiency of a (ideal) machine which uses the Carnot cycle: 1) work: along the adiabatic transformations, the sum of the works is 0; along the upper isothermal the work is positive, along the lower one is negative, therefore the total work VB is given by: W = R(TA −TC )⋅ ln VA 2) heat: it is exchanged only in the isothermal transformations; along the upper one is VB positive ( H a = RTA ⋅ ln ) and must be taken into account, along the lower one is VA VD negative( H r = RTC ⋅ ln ) and must be neglected. VC

Therefore the efficiency is given by: η = (6.7.21)

R(TA − TC )⋅ ln RTA ⋅ ln VB VA

VB VA

=

TA − TC T =1− C TA TA

On the other hand in every cyclic transformation the total work is equal to the total exchanged heat, i.e. to the difference between the absorbed heat H aand the released heat H r ; therefore: H W Ha − Hr η= = =1− r (6.7.22) Ha Ha Ha Hr T = C Equating (6.7.21) and (6.7.22) we get: (6.7.23) Ha TA Hr H = a That can be written also as: (6.7.24) TC TA $=8: Exercises Exercise 6.8.1. A volume VA contains n mole of a bi-atomic ideal gas, initially at temperature TA. Burning an amount M of methane, whose calorific power P (produced heat per unit mass) is 13271 [kcal/kg], the temperature is slowly doubled, simultaneously expanding the volume in order to maintain constant the ratio
1) 2) 3)

T2 . Assuming that no heat is wasted in the environment, find: V

The initial and final values of the pressure The work W produced by the gas. The value of M

DATA: n= 0.3 [mole]; R= 0.082 [litre*atm/(mole*K)] ; VA=9 [litre] ; TA=300 [K]; 1 [cal]=4.18[J]] Sol.
p A = 0.82
1 p A ≈ 0.41 2 V B = 36 pB = TB = 2T A = 600

1) V A = 9
T A = 300

2) W AB = 2nRT A

U AB = nC V (TB − T A ) =

5 R ⋅ T A ≈ 0,09945[Kc al] 2

3) H AB = U AB + W AB =
M =

9 R ⋅ T A ≈ 0,17901[Kc al] 2

H AB ≈ 1,34888E - 05[Kg] P

Exercise 6.8.1B. (Physics I - Exam June 5th 2008) A volume VA contains n mole of a monoatomic ideal gas, initially at pressure PA. It is heated or cooled along A,B,C,D,F,A maintaining constant the pressure and the volume alternatively, like in Fig. 2 Find: The values of pressure, temperature and volume in each point A, B, C, D, F. The works WAB, WBC, WCD, WDE , WEF WFA done by the gas in each branch AB, BC, CD, DE, EF,FA of the cycle 3) The total variation of the internal energy at the end of the cycle.
1) 2) P C D

A

DATA: n=1; CV= 3/2 R; PA = 1 [atm] ; VA=2 [litre] ; VB = 3 [litre] ; PC = 2 [atm] ; VD=5 [litre] ; PE = 0.5 [atm] R= 0.08205 [litre.atm /K.mole];

Β

F

E

V

Solution
pA =1 pB = p A VB = 3 p ⋅V V TB = A B = B T A nR VA
pC = 2 VC = V B = 3 TC = 73 ,17

1)

VA = 2

p ⋅V TA = A A nR p D = pC VD = 5 TD =121 ,95
p E = 0,5 VE =VD = 5 TE = 30 ,488

p F = p A = 0,5 VF = 2 TF = 12,195

W = pA (VB −VA );W =0 AB BC

2)

W = pC (VD −VC );W =0 CD DE W = pE (VF −VE );W =0 EF FA

3) ∆U = 0

Exercise 6.8.2. 3 A cube of steel has a volume V0 = 64[dm ] at temperature ϑ0 =20°in air. The density is 3 ρ = 7.83[Kg dm ] . The cube is heated until the temperature reaches ϑ1 =100°. The volumic dilatation coefficient is τ = 36 ⋅10 −6 [°C −1 ] . Find the work produced by the cube, the absorbed heat and the variation of internal energy. Solution The transformation is isobaric because the external pressure the atmospheric one p0 =1[atm . The work done by the steel can be measured as the work done by the external ] air and reads: W = p0 (V(ϑ1 ) −V(ϑ0 ) The final volume can be calculated using the dilatation formula: V(ϑ1 ) = V(ϑ 0 )(1+ τ (ϑ1 − ϑ 0 )) ⇒W = p0V0τ ⋅80 = 0.18432[litre⋅ atm ≈185[J ] ≈ 44[Kcal] ] The exchanged heat is given by: V(θ0 ) +V(ϑ1 ) H = cFeρ (ϑ1 −ϑ0 ) ≈ 5773[Kcal] ≈ 2.415⋅10 7 [J ] 2 The variation of internal energy is the difference: ∆U = H −W ≈ 5729[Kcal] Exercise 6.8.2B. A cylinder of ice of basis surface S and height h is contained in a cylinder of iron, whose internal volume has the same basis and height higher than h. The initial temperature of the ice is ϑ0 =0°. The iron cylinder is put in contact with a thermal source at high temperature, which transfers an amount of heat to the ice until half of the ice is transformed into water at ϑ0 =0°. Find the produced work, the absorbed heat and the variation of internal energy of the ice during the process. 3 3 DATA: ρice = 0.922[Kg dm ] ; ρW =1[Kg dm ] ; τice =1.53⋅10 −4 [°C−1 ] ; S = 1 [dm3]; h = 3 [dm]; latent heat λice = 80[Kcal Kg] Solution Exercise 6.8.3. (Physics I - Exam Sep 17th 2009) In a cylinder, whose walls are not adiabatic and one basis is a sliding piston, n moles of an ideal gas O2 are in equilibrium at temperature TA in a volume VA. The cylinder is slowly heated until it reaches a temperature TB, maintaining the pressure constant. Then the cylinder is slowly cooled down to the temperature TA, maintaining the volume constant. Finally the cylinder is put in a bath at constant temperature TA and the volume is slowly reduced to VA.
1)

Draw the cycle in a (P,V) plane (V being the abscissa)

2) 3) 4) 5)

Find the pressure PA in A Find the volume VB in B Find the total work WT produced by O2 in the cycle Find the variation UAB of internal energy from A to B n= 0.1 [mole]; ; VA=1 [litre] ; TA=300 [K]; TB=600 [K]; 1 [cal]=4.18[J] ; R= 0.082 [litre*atm/(mole*K)]
1 p A ≈ 0.123 2 =2

DATA:

Solution (pressure in atm, volumes in litre, work and internal energy in atm x litre )
p A = 0.246 p B = p A ≈ 0.246 VB = 2 T B = 2T A = 600
pC = VC

2,3) V A = 1
T A = 300

TC = T A = 300

W AB = p A (VB −V A ) ≈ 0.246 W BC = 0

4)

WCA = nRT A ln(

VC ) ≈ −0.246 ⋅ ln( 2) ≈ −0.17 VA
5 nR ⋅ T A ≈ 6.15[atm litre] 2

WT = W AB −WCA ≈ 0.076

5) U AB = nC V (T B − T A ) =

Exercise 6.8.4. A volume VA contains n mole of a monoatomic ideal gas, initially at pressure PA. The volume is enlarged very slowly up to VB maintaining the pressure constant. Then the container is put in contact with a thermostatic source which maintains the temperature of the gas constant and the volume is still enlarged up to VC. In the point C the container is separated from the thermostatic source and the volume is reduced to VD maintaining the pressure constant. Then the gas is put in contact with another thermostatic source at temperature TD and the volume reduced to VA. Find: 1) The values of pressure, temperature and volume in each point A, B, C, D 2) The works WAB, WBC, WCD, WDA done by the gas in each branch AB, BC, CD, DA of the cycle 3) The exchange heat HAB, HBC, HCD, HAD, in each branch of the cycle 4) The efficiency of the cycle 

DATA: n=1; CV= 3/2 R; PA = 1 [atm] ;  

VA=1 [litre]
pA =1 VA = 1

; VB = 1 [litre] ; VC = 1 [litre] ;
pB = p A VB = 1 p ⋅V V TB = A B = B T A nR VA

pC =

nRT C V B = pA VC VC VB TA VA

1)

p ⋅V TA = A A nR

VC = 1 TC = TB =

p D = pC = VD = V AVC VB

VB pA VC

TD = T A

2) W AB = p A (V B − V A ) = ...... > 0 V V W BC = nRT B ⋅ ln( C ) = p AV B ⋅ ln( C ) VB VB p V V V p V p V WCD = C C (V A − V B ) = p C ( A C − VC ) = C C (V A − V B ) = B B (V A − V B ) = p A (V A − V B ) = −W AB VB VB VB VB V V W DA = nRT A ⋅ ln( A ) = p AV A ⋅ ln( B ) VD VC Exercise 6.8.5. A volume VA contains n mole of a monoatomic ideal gas, initially at pressure PA. The container is put in contact with a thermostatic source, which maintains the temperature of the gas constant: the volume is enlarged very slowly up to VB. In the point B the container is separated from the thermostatic source and the pressure is reduced to PC maintaining the volume constant. Then the gas is put in contact with another thermostatic source at temperature TC and the volume reduced to VD. Finally the container is separated from the thermostatic source and the pressure is increased to PA maintaining the volume constant. Find: 1) The values of pressure, temperature and volume in each point A, B, C, D 2) The works WAB, WBC, WCD, WDA done by the gas in each branch AB, BC, CD, DA of the cycle 3) The exchange heat HAB, HBC, HCD, HAD, in each branch of a cycle 4) The efficiency of the cycle   DATA: n=1; CV= 3/2 R; PA = 1 [atm] ; VA=1 [litre] ; VB = 1 [litre] ; VC = 1 [litre] ; Solution  

 

Exercise 6.8.6. A cylinder of volume VA contains n mole of an ideal gas (O2), initially in equilibrium at temperature TA. One of the basis of the cylinder is a sliding piston. The cylinder is put in contact with a thermostatic source (a basin of water) having a constant temperature TB and the pressure is maintained constant until the gas reaches the temperature TB . Then the pressure is lowered very slowly to the value PC maintaining the cylinder inside the basin of water at constant temperature. Finally the cylinder is put in contact with another thermostatic source (another basin of water) having a constant temperature TD = TA and the pressure is again maintained constant until the gas reaches the temperature TD . Draw the 3 thermodynamic transformations AB, BC, CD in the plane PT (P ordinate and T abscissa) 2) The total transformation ABCD is cyclic? Why? 3) Write the values of the volume, pressure and temperature in each point A, B, C, D 4) Find the works WAB, WBC, WCD done by the gas in each branch AB, BC, CD of the transformation 5) Find the total variation UAD of the internal energy from A to D
1)

Data: n=0.12 [mole]; VA=1[litre] TA=300[K]; TB = 400 [K]; PC = 1 [atm]; R= 0.08205 [litre.atm /K.mole];

Solution 1)

2)

No

pA ≈ 3

pB = p A TB = 400 nR ⋅ TB T VB = = B PA PB TA pD =1 VB = 1,33 TD = T A = 400 V D = 3,958

3)

VA = 1 p ⋅V T A = A A = 300[ K ] nR

pC = 1 TC = TB = 400 VC = 3,938

W AB = p A (V B − V A ) = 0,9846

4) W BC = nRT B ⋅ ln(

VC ) = 4,2656 VB

WCD = p C (V D − VC ) = −0,984 5) U AD = 0

Exercise 6.8.7. A cylinder of volume VA contains n mole of an ideal mono-atomic gas, initially in equilibrium, and is in contact with a thermostatic source (a basin of water) having constant temperature TA . One of the basis of the cylinder is a sliding piston and the pressure is increased very slowly until the gas reduces the volume to VB, remaining in contact with the water. Then the cylinder is put in contact with another thermostatic source (another basin of water) having constant temperature TC and the volume is maintained constant until the gas reaches the temperature TC. Finally the pressure is reduced very slowly until the gas reaches the volume VD, equal to the initial one VA , remaining in contact with the water and maintaining the temperature TC . 1) Draw the 3 thermodynamic transformations AB, BC, CD in the plane VT (V ordinate and T abscissa) 2) Is the total transformation ABCD cyclic? Why? 3) Write the values of the volume, pressure and temperature in each point A, B, C, D 4) Find the works WAB, WBC, WCD done by the gas in each branch AB, BC, CD of the transformation 5) Find the total variation UAD of the internal energy from A to D DATA: n=0.12 [mole] ; VA=4 [litre] TA=300 [K] ; VB = 2 [litre] ; TC = 400 [K] ; R= 0.08205 [litre.atm /K.mole]; CV= 3R/2; Solution

1) 2)

No

p A ≈ 0.73

p B = 1.47 TB = 300 VB = 2

pC = 1.96 TC = 400 VC = 2

p D = 0.98 TC = 400 VC = 4

3) V A = 4
T A = 300 [ K ]

W AB = nRT A ⋅ ln(

VB ) = −2,047 VA

4) W BC = 0
WCD = nRT C ⋅ ln( VD ) = 2,729 VC = n ⋅ Cv ⋅ (TD − T A ) = 12 ,305

5) U AD

Exercise 6.8.8. (Physics I - Exam April 30th 2007 ) A volume VA contains n moles of an ideal gas at temperature TA. The gas is cooled down to the temperature TB following the line AB shown in the TV diagram of the figure. Then the volume is expanded up to a volume VC along the line BC; it is heated again up to the temperature T D= TA, maintaining the volume constant and finally the gas goes again to the state A as shown by line DA. All these transformations occur very slowly. Find: a) The values of pressure, temperature and volume in each point A, B, C, D. b) The work LAB performed by the gas, the variation of internal energy U AB and the exchanged heat QAB in the transformation AB c) The work LBC performed by the gas, the variation of internal energy U BC and the exchanged heat QBC in the transformation BC d) The work LCD performed by the gas, the variation of internal energy U CD and the exchanged heat QCD in the transformation CD e) The work LDA performed by the gas, the variation of internal energy UDA and the exchanged heat QDA in the transformation DA

n = 0.5 VA = 2 litre TA = 300 K TB = 100 K VC = 2 VA CV = 3R/2 Solution

$=9: The II Law of Thermodynamics

The thermodynamic machines offer the possibility to transform heat into work: the thermodynamic system receives heat (e.g. burning some fuel) and produces work to be used by other external mechanical systems. As we saw in the Carnot cycle, a certain amount of the heat supplied to the thermodynamic system is given back to some environment at lower temperature and this is the reason why the efficiency in the transformation “heat into work” is not equal to the unit. A lot of efforts have been done mainly in the nineteenth century to find machine having a high value of efficiency (the dream was to get η =1 ). The high number of observations connected to these trials led to the discovery of the II principle of the thermodynamics. It is noteworthy that 2 statements were found (nearly independently upon each other) of this law, by Clausius and Lord Kelvin. These 2 statements look very different from each other. Nevertheless they are equivalent: if one statement is true, the second one cannot be false (and viceversa). In other words if one statement is accepted as Law also the other one must be accepted as Law. Clausius statement (CS) of the II Law of Thermodynamics “Heat transfer from a body at lower temperature to a body at higher temperature cannot be spontaneous (i.e. it requires some negative work)” Kelvin statement of the II Law of Thermodynamics “All the existing thermodynamic cyclic machines, which exchange heat with only one source at a fixed temperature, cannot produce positive work (i.e. work that can be used by external systems) ” Equivalence of Clausius and Kelvin statements For sake of brevity let’s call Clausius the Clausius statement and let’s call Kelvin the Kelvin statement Equivalence means that the statements are either true or both false: if we accept one of them, as consequence of the observations, as a law, we must accept also the other. To prove the equivalence first a) we assume Kelvin as true and shall prove that Clausius cannot be false and then b) we assume Clausius as true and shall prove that Kelvin cannot be false Hypothesis: Kelvin is true. If, simultaneously, Clausius is false, heat could transfer from a colder body to a hotter body without requiring work. Let’s now consider a Carnot machine in which H1 is the negative heat released to the lower temperature source during the lower isothermal: Clausius being false, we can connect the lower temperature source to the upper one in such a way that an amount H1 of heat flows spontaneously from the lower to the upper source. In this way the total machine (Carnot machine + connection) can produce work (by the Carnot machine) basically without using the lower temperature source ( H1 being returned to the higher source by the connection) b) Hypothesis: Clausius is true. If, simultaneously, Kelvin is false, we can build a machine which, absorbing H heat from a lower temperature source, produces a positive work W . We can consume completely this work to move friction
a)

forces (dissipative work) inside a system at higher temperature and in this way the total work is zero but an amount H of heat transfers from lower to higher temperature. Refrigerating Machines Before discussing the basic consequences of the II principle of the thermodynamics, we discuss a particular kind of cyclic machines. A cyclic machine, which works between 2 thermal sources and extracts an amount of heat from the higher temperature source releasing a smaller amount of heat to the lower temperature source, produces a positive mechanical work equal to the difference between absorbed and released heat. If the transformations are reversible, it is possible to invert the direction of the cycle. The total work of the inverse cycle is negative because each infinitesimal transformation dV has opposite sign and the corresponding infinitesimal work p⋅dV too. Also each infinitesimal variation of internal energy is opposite and consequently each infinitesimal exchanged heat. Therefore the heat exchanged with low temperature is positive and that one with high temperature is negative, i.e. some heat is transferred from lower to higher temperature, accompanied by some work transformed into heat. It must be remarked that transfer of heat from higher to lower temperature is a trivial consequence of the 0-th principle and doesn’t require any cyclic machine but only a connection. The inverse cyclic machine shows another possibility: to move heat from lower to higher temperature source if some mechanical work is spent. This feature is peculiar of the so-called “Refrigerating Machines”, whose typical examples are fridges and freezers. Here 2 examples of Refrigerating Machines are shown. Example n. 1: Inverse Carnot cycle Let’s consider the Carnot cycle (see Chapter 6, $=7) operating in opposite direction: an adiabatic expansion AD, an isothermal expansion DC, an adiabatic compression CB and an isothermal BA. The negative (received) work is given by: V V W +W = −CV (TA −TC ) − R⋅TA ⋅ ln B and an amount of heat H DC = R⋅TC ⋅ ln B is CB BA VA VA absorbed from the lower temperature source. Of course the efficiency of a refrigerating machine is different with respect to the efficiency of a machine producing work. In fact the goal of a refrigerating machine is to extract as much heat as possible from a thermal source spending as few mechanical work as possible. Therefore the efficiency of a Refrigerating Machine is defined as:
Ha W xt e H a is the absorbed heat and W xt is the modulus of the mechanical received work where e (i.e. the negative work of the cycle, which is consumed by the inverse machine).

ηRM =

In the case of the “inverse Carnot cycle” the efficiency is given by:

ηRM =

Ha H DC 1 = = = W W +WBA C (T − T ) + R⋅T ⋅ ln VB 1+ TA − TC ⋅ ln( VB )γ −1 ext CB V A C A VA TA VA

R⋅TC ⋅ ln

VB VA

Example n. 2: Inverse cycle of Exercise 6.8.5 A volume VA contains n mole of a monoatomic ideal gas, initially at pressure PA. The cycle starts with the isovolumic transformation AD, then expands the volume along the isothermal DC, then again reaches the point B along an isovolumic and finally goes back to Aalong an isothermal. Find: 1) The values of pressure, temperature and volume in each point A, B, C, D 2) The works WAD, WDC, WCB, WBA, done by the gas in each branch AD, DC, CB, BA of the cycle 3) The exchange heat HDA, HDC, HCB, HBA, in each branch of a cycle 4) The efficiency of the cycle  DATA: n=1; CV= 3/2 R; PA = 1 [atm] ; VA=1 [litre] ; VB = 1 [litre] ; VC = 1 [litre] ;  

   Solution

Irreversible Refrigerating Machines Also an irreversible cycle can extract heat from lower temperature to higher temperature sources but, of course, this cycle cannot be inverted. The efficiency is defined as for the reversible case: we see the relation between the efficiency of irreversible and reversible cycles in the following. Carnot theorem

All irreversible machines operating between 2 thermal sources at temperatures TH >TL have efficiency lower than the reversible ones operating between the same temperatures: and the reversible machines have all the same efficiency. Proof Let SH and SL be two thermal sources at temperatures TH >TL . Let M, M ( R) be two cyclic machines, which extract in each elementary cycle the amounts of heat h and h( R) H H ( SH and release the amounts of heat h and hLR) respectively to SL . The respectively from L ( R) second machine M is reversible, the first one M can be reversible or irreversible. In ( R) general hL ≠ hL : we can find 2 integer numbers m and n such that ( ( m⋅ hH = n⋅ hLR) ≡ H L ≡ H LR) . Considering a cycle of M as made by m elementary cycles of M and a cycle of M ( R) as made by n elementary cycles of M ( R) (a multiple of a cycle is still a cycle), both machines release the same amount of heat to the lower temperature source.

Fig.6.9.1.a

Fig.6.9.1.b

During a “direct” cycle (see Fig 6.9.1a) the produced works are:
W = HH − HL > 0
( ( ( W( R) = H HR) − H LR) = H HR) − H L > 0

(6.9.1)

( ( where H HR), H LR), H L , H L are taken as positive.

( If M ( R) is operating in the “inverse” cycle, as a refrigerating machine, H LR) becomes the ( extracted heat from SL and −H HR) becomes the released heat to SH (see Fig 6.9.1b) and the produced work by M ( R) is negative. Let’s now consider the “total” machine made by both M and M ( R) (this one operating in inverse cycle) and the lower temperature source SL (see remark below). This machine works with only one source SH , because the other SL receives and releases the same amount of (R) heat H L = H L , therefore it behaves just as temporary heat storage. The total work W T made by the total machine must be negative or null, because of the Kelvin statement: ( ( ( W = (H H − H L ) + (H LR) − H HR) ) = H H − H HR) ≤ 0 T From eq. (6.9.2) a lot of inequalities come:

(6.9.2)

(R) (R) 0 ≥ HH − HH ⇒ HH ≤ HH ⇒

( H L H L H LR) ≥ ( R) = ( R) ⇒ HH HH HH

(R) (R) H H (R) H − HL HH − HL ⇒ 1− L ≤ 1− L ⇔ H ≤ (R) ( HH HH HH H HR) Recalling eq. (6.9.1) for directs cycles of M and M ( R) , from (6.9.3) we obtain the following

(6.9.3)

relationship between the efficiencies:

W W( R) η= ≤ ( R) = η ( R) (6.9.4) HH HH Eq. (6.9.4) states that a reversible machine operating between 2 thermal sources has efficiency not less than any other machine operating between the same 2 sources. In particular, if also M is reversible we can repeat the previous proof with M playing the role of M ( R) and viceversa: in this case inequality (6.9.4) should be inverted: in order to be valid in both cases the only possibility is the equality. This means that all reversible machines operating between the same 2 temperatures have the same efficiency: remembering that a Carnot machine is reversible, we can write the efficiency of all reversible machines operating (direct cycle) between TH and TL is given by: T η( R) =1− L (6.9.5) TH Concerning the irreversible machines, the efficiency must be not greater than that one of the ( reversible machine, since eq. (6.9.5): in principle it could be also equal, when H H = H HR) . In the real cases, friction is always present in the mechanical pieces of the thermodynamic system and spends part of the produced work W to create heat into SL : in this way H H increases and equality becomes inequality. Summarizing: all irreversible machines have efficiency lower than the reversible ones. The reversible machines have the same efficiency.
Remark about cyclic machine containing a source

A question could arise after the statement that the total machine includes a thermal source: when this is permitted? The answer is the following: a thermal machine, composed by thermal parts (gas…) and mechanical parts (containers, sliding pistons…) can contain also some mass, like gas, water or solid…, which some heat can flow into or from. But the total heat, which enters and exits in a cycle, must be equal to 0: otherwise the machine is not cyclic because in each cycle the temperature of the mass increases or decreases.

Clausius inequality Up to now we dealt with machines operating between 2 sources: in this paragraph we will examine the behaviour of reversible and irreversible machines operating with more than 2 sources, which receive or release heat. Let’s consider a machine (reversible or irreversible), which exchanges cyclically N amounts H i of heat with a set of N sources S at temperature T , producing a work W (see the i i H i are positive (absorbed by M ) and some are negative right part of fig.6.9.2). Some of (released by M ). From the I Law of thermodynamics we can write:
W = ∑Hi
i N

(6.9.6)

Let’s now suppose to connect a reversible machine R with each source S and with another i i source S' at temperature T ' and suppose that, choosing suitably the cycles as in proving the Carnot theorem, the amount of heat exchanged with S is equal and opposite to that exchanged i H by the machine M (see the left part of Fig. 6.9.2): we shall call this heat − i , keeping in mind that the sign minus doesn’t mean that the heat is negative, but just that it is opposite to that exchanged by M .

Fig. 6.9.2

Let H 'i and W be the exchanged heat and the produced work by R with the source S . i i i For each Ri we can write: W = H 'i − H i i (6.9.7) The total machine composed by M , all the reversible machines R and all sources S (these i i sources can belong to a machine because they receive and release the same amount of heat) is operating only with S' . Therefore the total work W made by the total machine must be T negative or null, because of the Kelvin statement and using (6.9.6) and (6.9.7):
0 ≥W =W + ∑ i = ∑Hi + ∑(H 'i − H i ) =∑H 'i ⇒ W T
i i i i N N N N

H' ⇒∑ i ≤ 0 T' i

N

(6.9.8)

Each R is reversible: from the definition of efficiency and from the property of reversible i machines (eqs. (6.9.3) and 6.9.5)) we can write:

η

( R)

( ( ( ( (R) (R) TL H HR) − H LR) H LR) TL H LR) HH HL = 1− = = 1− ( R) ⇒ = ( ⇒ = ( TH H HR) HH TH H HR) TH TL

(6.9.9) Last equation in (6.9.9) indicates that the ratio of the absolute value (remember that ( ( H HR), H LR) were taken as positive in the Carnot theorem proof) of the exchanged heat to the temperature is a constant ratio. Remembering that, in a reversible machine operating between 2 sources, one exchanged heat is positive and the other one is negative, for machine R we can i write:

H 'i −(−H i ) H i = = T' Ti Ti
(6.9.10) which is valid in both cases: if Hi > 0 (heat absorbed by M ) then −Hi < 0 (heat released by R ) and H 'i > 0 , the ratios in (6.9.10) are positive, as in (6.9.9); if Hi < 0 (heat released i by M ) then −H i > 0 (heat absorbed by Ri ) and H 'i < 0 , the ratios in (6.9.10) are both negative and equation (valid for absolute values) is valid again. Using eq. (6.9.10), eq. (6.9.8) becomes:
N N H' H 0 ≥∑ i =∑ i T' Ti i i

(6.9.11)

which is said: Clausius Inequality. This inequality states that, when a machine exchanges some amounts of heat with some sources in a cycle, the sum of the ratios between the exchanged heat and the temperature of the exchanging source cannot be positive. The inequality symbol ≥ in (6.9.11) comes from the Kelvin statement: if the machine is reversible the equality symbol is valid because the machine in the inverse cycle must produce again a work opposite to that direct, which means work equal to 0. If the machine is irreversible the strict inequality symbol is valid, due to the reasons discussed in the Carnot theorem proof. The total machine is reversible or irreversible if M is reversible or irreversible, because all the other machine, which compose the total machine, are reversible. The Entropy Clausius inequality refers to a cyclic machine, which exchanges heat with a finite number, greater than 2, of thermal sources. One can also suppose this number be infinite, δH i (T) being the infinitesimal amount of het exchanged by the machine with each source. In Exercise n…. an example of transformation, in which heat is exchanged with a source continuously varying the temperature, is shown. In this case the Clausius inequality becomes a (cyclic) integral over all points of the cyclic transformation:

(6.9.12) T T Let point A be the starting (equilibrium) position in the Clapeyron plane (V,P) and B another point along the cyclic path: let’s call γ the path from A to B and γ2 the remaining path to 1 reach again A from B in the cycle:
i=1

0 ≥∑

N

δHi (T)

→0 ≥  ∫

δH(T)

Fig.6.9.3 Let’s first suppose that both inequality is , i.e. :

=

γ 1

and γ2 are reversible. In this case the sign in Clausius

B B δ H (T) δ H(T) A δ H (T) δ H(T) A δH(T) =0 ⇒ ∫ − ∫ =0 ⇒ ∫ = ∫ (6.9.13) ∫  T T T T T A,γ B,γ A,γ B,γ
1 2 1 2

Since the paths

can be all possible continuous curves joining A to B, eq. (6.9.13) δH (T ) says that the integral ∫ is independent on the path γ. T A,γ Therefore we can write the differential integrand as: δH ≡ dS (6.9.14)
B

γ and γ2 1

T

Symbol d is used instead of δ because of the independence on the path. The quantity S is called “Entropy”.

Summarizing: the variation of entropy dS is the ratio of the exchanged heat by a machine to the temperature of the thermal source, from which heat is received or given, provide that the transformation is reversible. If the cyclic transformation is irreversible, i.e. contains a part of the path which is irreversible, the Clausius inequality is a strict inequality. Let assume that from A to B the path γ is the 1 reversible part and from B to A the path γ2 is the irreversible part. The Clausius inequality can be written as:
B

A,γ1re v

δH(T)
T

+

B,γ2irr

A

δH(T)
T

=

A,γ1re v

B

δH(T)
T

A,γ2 irr

B

δH(T)
T

<0

(6.9.15)

Keeping in mind that the Clausius integral along a reversible path is the entropy variation, eq. (6.9.15) becomes:

B,γ2irr

A

δH(T)
T

<

A,γ1rev

B

δH(T)
T

= S(B) − S(A)

(6.9.16)

Remarks: 1. Obviously, in eq. (6.9.16) the sign “ - “ can only be assign to the integral of the reversible path, because it is the only path of the cycle that can be reversed A δH (T) 2. The integral ∫ T is not a variation of entropy: it is called “Clausius B,γ2irr Integral” Eq. (6.9.16) states that: when a thermodynamic system transforms from an equilibrium point A to an equilibrium point B, the Clausius Integral has the same value if the transformation is reversible and is called “Variation of Entropy”; if the transformation is irreversible it has a lower value. Remark: the variation of entropy in an irreversible transformation is the variation of entropy of a reversible transformation between the same initial and final (equilibrium) states.

$=10: Exercises on II Law of Thermodynamics
Exercise 6.10.1. A cylinder, having a sliding piston as upper basis, contains n moles of ideal O2 gas. The piston and the lateral basis are insulators with respect the heat transfer and the lower basis is conducting. At the beginning the gas volume is VA and temperature TA in equilibrium. The

lower basis is covered by an insulator slab and the volume is expanded very slowly up to the temperature becomes TB. Then the slab is taken away and the cylinder is put in contact with a source at constant temperature TC, maintaining the volume constant. When the equilibrium is reached in the point C, the insulating slab is put again on the lower basis and the volume is slowly diminished to the original VA. Then the slab is taken away and the cylinder is put in contact with a source at constant temperature TA, maintaining the volume constant until the gas reaches the equilibrium. Find:
1)

Volume and temperature in A,B,C,D
a. b. c. d.

2) Exchanged heat HAB, produced work WAB and internal energy variation UAB along AB Exchanged heat HBC, produced work WBC and internal energy variation UBC along BC Exchanged heat HCD, produced work WCD and internal energy variation UCD along CD Exchanged heat HDA, produced work WDA and internal energy variation UDA along DA 3) The efficiency η of the cycle: is it less than a Carnot cycle operating between both sources? 4) The entropy variation SBC and SDA along the 2 iso-volumic branches DATA: n= 0.3 [mole]; R= 0.082 [litre*atm/(mole*K)] ; VA=1 [litre] ; TA=450 [K]; TB=350 [K]; TC=300 [K]; 1 [cal]=4.18[J]] Solution
7 5 1) V = 1 A

γ=

TB = 350 V B =V A ( TA ) TB
1 γ− 1

VC = V B TC = 300

VD = V A TD = TC ( TA ) TB

T A = 450

H AB = 0;W AB = −U AB = −nC V (TB − T A ) > 0 W BC = 0; H BC = U BC = nC V (TC − TB ) < 0

2)

H CD = 0;WCD = −U CD = −nC V (TD − TC ) = −nC V W DA = 0; H DA = U DA = nC V (T A − TD ) > 0

TC (T A − TB ) < 0 TB

3) η =

WAB +W T CD <1− C H DA TA

4) let’ call SBC and IBC the entropy variation and Clausius integral respectively, we recall that C δH I BC ≡ ∫ in , T is the temperature of the source which heat is exchanged with, i.e. T
B ,unrev

T

= TC. Therefore: C δH
I BC ≡
B ,unrev

TC

=

C nC V nC V ⋅ ∫ dT = ⋅ (TC − TB ) TC B ,unrev TC

The entropy variation must be calculated choosing a reversible transformation between the same boundaries B and C: we can choose the reversible isovolumic transformation in which the gas from B to C is put in contact with several sources each one increasing by a differential amount from TB to TC, i.e.: C C TC δH dT
S BC ≡
B , rev

T

= nC V ⋅

B , rev

T

= nC V ⋅ ln(

TB

)

and it is easily shown that: SBC > IBC. Analogous demonstration for DA:
I DA ≡ S DA ≡

D ,unrev

A

δH
TA T

A nC V nC V = ⋅ ∫ dT = ⋅ (T A − TD ) T A D ,unrev TA

D , rev

A

δH

= nC V ⋅

D , rev

A

T dT = nC V ⋅ ln( A ) T TD

and again : SDA > IDA. 3) U = 0

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