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 (lets call it V(0) ) and the same with boiling water (lets call it V(100) ), the temperature [C] will correspond to a dilated volume (6.1.1) V () = V (0) + ( V (100) V (0)) 100 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 . 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, lets rewrite the Gay-Lussac law for ideal gases:
V = const
(at

constant pressure)

(6.1.2)

as: (6.1.3) V () V (0) = const ( 0) V () = V (0) + const ( 0) = V (0)(1 + ) -1 The value of =1/(273.15 +-0.01) (C ) is the same for all ideal gases and from (6.1.3) we deduce that temperature has a minimum at min =273.15 (C). A scale using the same unit (degree centigrade) but the 0 value at 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 (
i i i =1

f ) = 0

(6.1.4)

where mi and 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), f is given by the following relationship:

f =

m c
i i i =1 n

(6.1.5)

m c
i =1

i i

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

(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 = m, where is a (nearly) constant parameter called latent heat for the specific process and depends on the bodys material and, of course, on the process.

$=2: Exercises about calorimetry

Exercise 6.2.1 In a vessel containing a mass m1 of water at temperature ! 1 , another mass m2 at temperature ! 2 is added. After a long time the final temperature of the whole water is ! f but the transformation is not adiabatic. How much heat has been released to the vessel? DATA: m1 =1.5 [kg]; m2 =2.5 [kg]; ! 1 =50 [kg]; ]; ! 2 =15 [C]; ! f =20 [C]; Exercise 6.2.2

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, 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, A , MB, cB, B) are put all together in an insulated container, what will be the final situation in terms of temperature and masses? Lets suppose that the temperature of the change of state for A and B is c and that for all the other bodies are outside the range of i. Lets also suppose that the change of state from A to B requires heat and be the corresponding latent heat. Solution: The 0-th law states that after enough time the temperature will be uniform, doesnt matter which way. Therefore we are free to imagine every temporary exchange of heat among all bodies before they reach the equilibrium. Lets imagine the following steps: Step 1: all bodies reach the temperature c; the total heat Qexcess absorbed or emitted by the bodies is defined as:

Qexcess mi ci ( i c )
i =1

Step 2: if Qexcess is positive means that at 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: lets calculate the total heat QAB = MA , required for changing all MA into the state B and compare it with Qexcess: a) If: Qexcess < QAB : the final temperature will be c and MAB = Qexcess / 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 c to f without further changes of state. The final temperature f will be found using Eq.(6) with i = c and cB holding for the total mass MA + MB.

Qr = [mi ci + ( M A + M B )c B ]( f c )
i =1

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 1 is put over another cube of lead of mass m2 and temperature 1 , which in turn is put is put over another cube of silver of mass m3 and temperature 3. All the system is in a vacuum chamber (a totally empty container) whose floor is adiabatic, i.e. doesnt 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] ; 1= 20 C; 2= 200 C; 3= 120 C (Sol.: f=110.253) Exercise N.6.2.5 A cube of ice of mass m1 and temperature 1 is put inside a cup of water. The mass of the water is m2, its temperature is 2 and the cup is adiabatic. Find the final temperature at the equilibrium. Data: m1= 0.4 [Kg] ; m2= 2.5 [Kg] ; 1= -20 C; 2= 60 C Exercise N. 6.2.6 A mass m1 of ice at temperature 1 is put inside a cup of water. The mass of the water is m2, its temperature is 2 and the cup is adiabatic. Find the final temperature at the equilibrium. Data: m1= 0.4 [Kg] ; m2= 1.5 [Kg] ; 1= -20 C; 2= 20 C Exercise N. 6.2.7 In the exercise 4.1.2 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] ; 1= -20 C; 2= 20 C

Exercise N. 6.2.8 In the Exercise N. 4.1.1 the floor is not adiabatic and when the masses reach the termodynamical 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 Lets consider a thin layer of infinitesimal thickness dx and large finite surface S, perpendicular to the x axis: lets suppose that the temperature is the same on all the surface passing through x. On both sides of the layer the temperature is !(x) and !(x + dx) = !(x) + d! 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 d! and inversely proportional to dx :
dQ = !kS d" dt # dx dQ d" = !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 Lets consider a body at temperature ! B , whose surface S is surrounded by a gas at temperature !G : heat flows from the body to the gas or viceversa obeying the following law: dQ (Newton law) (6.3.2) = h S dt where: h = external heat transfer coefficient (or Newton coefficient) !" # " B $ "G = 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 = T 4
Where:

(Stefan law)

(6.3.3)

W is the heat emitted per unit time and unit surface. = Stefan constant ( ! ! 5.67 "10 #8 [W " m #2 " K #4 ] for black body) T = body temperature Exercise N. 4.2.1 An iron heater contains hot water, which flows through, at constant temperature in. The heater is inside a big room whose temperature 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: in= 60 C; 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 in) to the external water (where temperature is out). Recalling that the at equilibrium hypothesis requires:

dH d = 0 H = H (t ); = 0 = ( x) , dx dt write:
out in

and that (x) is a continuous function, we can

d =

out

in

and solve the Eq.(4.3.1) of the internal heat transfer (Fourier law):

dH d d 1 dH = kS = out in = dt dx dx kS dt
x=d

out

in

d =
0

d dx = dx

x=d

x =0

kS

1 dH dx = dt

1 dH d dH dH kS kS dx = = ( in out ) H = ( in out ) 3600[ s ] kS dt x =0 kS dt dt d d

Exercise N. 4.2.2 The same heater of the Exercise N. 4.2.1 is completely dipped in an adiabatic basin containing a mass m of hot water initially at temperature 0. The internal water, which flows inside the heater is maintained always at the same temperature 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 temperaure is always uniform. Find the temperature of the outside water after a time t. Data: in= 80 C; 0= 10 C; S = 10 m2; d = 3 mm; t = 40 [s]; m = 200 [kg] Solution: As in Exercise N. 4.2.1 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 dt = m c d , dt where c is the specific heat of the water. Taking into account that the external water temperature = (t ) is a function of the time. Going ahead in the solution of the Fourier equation: (t ) d x=d 1 dH 1 dH dH kS (t ) 0 = d = dx = dx = ( in (t )) kS dt kS dt x =0 dt d in 0 Using also the equation of calorimetry we get the system: dH kS kS dt = d ( in (t )) t d mc whose solution in (t) is: (t ) = in + ( 0 in ) e dH = dH dt = m c d dt dH =

Thermodynamical parameters of some material

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 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

1538

65

2862

1620

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

. -3

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 . -4 5.3 10 . -5 5.6 10

. -3

$=4:Thermodynamical transformations
Thermodynamical systems can be described by macroscopical 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 indipendent 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 doesnt transform chemically 3) each part of the system has the same temperature the system is said to be in thermodynamical equilibrium. Transformations When a system changes the values of (P,V,T) we say that it undergoes to a thermodynamical transformation. A finite thermodynamical transformation from the state (P0,V0,T0) to the state (P1,V1,T1 ) proceeds through infinitesimal changes (dP,dV,dT) of the thermodynamical quantities. If the initial and final states are the same the transformation is called cyclic transformation. Reversibility of the thermodynamical transformations When a thermodynamical 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 thermodynamical transformation requires to be very slow: slow transformation is usually assumed as synonymous of reversible. Special transformations 1) Adiabatic transformation: the thermodynamical system does not receive nor gives any heat 2) Isothermal transformation: the thermodynamical system maintains its temperature constant during the transformation 3) Isobaric transformation: the thermodynamical system maintains its pressure constant during the transformation

4) isovolumic transformation: the thermodynamical system maintains its volume constant during the transformation 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 thermodynamical system) and negative if made by outside on the system (shrinking of the thermodynamical system). For a thermodynamical 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 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 thermodynamical 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: P T = const Find pressure and temperature when temperature becomes twice the initial one and the work done by the thermodynamical system.

$=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 (VB,PA,TB):

W AB = dW = P dV = 0
A A

(6.5.1)

Remarks: in an isovolumic transformation the work of an ideal gas is 0. Its easy to see that this result holds for all thermodynamical systems. 2) Isobaric transformation from (VA,PA,TA) to (VB,PA,TB):
B B B

W AB = dW = P dV = P dV = P (VB V A )
A A A

(6.5.2)

Remarks: in an isobaric reversible transformation the work is given by P.V. Its easy to se that this result holds for all thermodynamical systems 3) Isothermal reversible transformation from (VA,PA,T) to (VB,PB,T): B B B V nRT dV (6.5.3) W AB = dW = P dV = P dV = nRT = nRT ln( B ) V V VA A A A A Remark: we profited of the reversibility property using the equation of state, which holds only for equilibrium gases.
B

Ex1. 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: 1) The values of pressure, temperature and volume in each point A, B, C, D, F. 2) 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.
P C D

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];

Solution

pA = 1
1) V A = 2

pB = p A VB = 3 TB = p A VB VB = TA nR VA

pC = 2 VC = VB = 3 TC = 73,17

p D = pC VD = 5 TD = 121,95

TA =

p A VA nR

p E = 0,5 VE = VD = 5 TE = 30,488
W AB = p A (VB V A ) = WBC = 0
2)

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

WCD = pC (VD VC ) WDE = 0 WEF = p D (VF VE ) WFA = 0

$=6: The I law of Thermodynamics

Q = L + dU
Units: 1 Kcal = 4184 J = 1000/0.239 J (6.6.1)

$=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 indipendent and the 3-th is deduced from the equation of state): (6.7.1) U = U (V , p, T ) From the Analysis we know that the infinitesimal variation of U is given by: U (V , p, T ) U (V , p, T ) U (V , p, T ) (6.7.2) dU = dV + dp + dT V p T Joule experiment was made in this way: 2 identical spheres were connected by a pipe and a sectum 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 sectum 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, no heat was excanged by the gas with the external world: H = 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 thermodynamical law we U (V , p, T ) U (V , p, T ) U (V , p, T ) deduce: 0 = dU = (6.7.3) dV + dp + dT V p T 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 doesnt 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 ) 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 it easier to use as a measure of the amount of a gas its number of moles instead of its 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 Lets calculate the spacific 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: (6.7.4) Where the symbol 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:

H = CV d

CV =

H
d

pdV + dU dU = d d

(6.7.5)

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

pdV + dU pdV dU Rd = + = + CV d d d d d From this formula we can get the Mayer theorem: C p = CV + R Cp = =

(6.7.6)

Work , heat and internal energy in special transformations of an ideal gas Lets suppose that 1 mole of gas initially in the state A (VA, pA, TA) undergo to 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:

H = pdV + dU = CV d
B

(6.7.7)

W A, B = pdV = 0
A B B

U ( B ) U ( A) = dU = CV d = CV [( A) ( B )]
A A B B

(6.7.8)

H A, B = H = dU = CV [T A TB ]
A A

Isobaric transformation
B B

W A, B = pdV = p A dV = p A [V B V B ]
A A B B

U ( B) U ( A) = dU = CV d = CV [T A TB ]
A A B B B

(6.7.9)

H A, B = H = pdV + dU = p A [V B V B ] + CV [T A TB ]
A A A

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

B B

U ( B) U ( A) = dU = CV d = 0
A A B B B B

(6.7.10)

H A, B = H = pdV + dU = pdV = RT A ln
A A A A

VB VA

Adiabatic reversible transformation ( H = 0 ) Before calculating WA,B, HA,B and U(B)-U(A), we can deduce the equation of an adiabatic curve, C using the I law. Lets define p . CV

H = 0 = pdV + dU pdV = dU = CV dT
Using the equation of state, we can write Eq. (4.7.11) as:

(6.7.11)

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
Cp

R CV

T = const

R CV

Using the Mayer theorem:

CV

T = TV 1 = const

(6.7.13)

And using the equation of state:

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

(6.7.14)

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

U ( B ) U ( A) = dU = CV d = CV [T A TB ]
A A B

(6.7.15)

H A, B = H = 0
A

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. Lets 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
(6.7.16)

U ( B ) U ( A) = 0 H A, B = RT A ln
Adiabatic transformation BC
C C

VB VA

W B ,C = pdV = dU = CV [TC T A ]
B B C C

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

(6.7.17)

H B ,C = H = 0
B

Isothermal transformation CD

WC , D = RTC ln

V VD = RTC ln C VC VD
(6.7.18)

U ( D ) U (C ) = 0 H C , D = RTC ln
Adiabatic transformation DA
A A

V VD = RTC ln C VC VD

WD , A = pdV = dU = CV [T A TC ]
D D A A

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

(6.7.19)

H D , A = H = 0
D

Using the equation (4.7.13) for BC and DA adiabatic transformations, we get:

TAVB

1 1

= TCVC

1 1

TCVD

= TAV A

VB VC = V A VD

(6.7.20)

Using (4.7.20) , from (4.7.16) and (4.7.18) 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 substitution: R nR; CV nCV Efficiency The efficiency of a cyclic machine is defined as the ratio of the total work made by the machine in one cycle to the absorbed amount of heat. $=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 T2 constant the ratio . Assuming that no heat is wasted in the environment, find: V 1) The initial and final values of the pressure 2) The work W produced by the gas. 3) 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) V A = 9

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

T A = 300
2) WAB = 2nRTA

U AB = nCV (TB T A ) =

5 R T A 0,09945[Kcal] 2

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

9 R T A 0,17901[Kcal] 2

H AB 1,34888E - 05[Kg] P

Exercise 6.8.2. 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) 2) a. b. c. d. Volume and temperature in A,B,C,D

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 of the cycle: is this less than a Carnot cycle operating between the 2 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 A = 1

TB = 350 VB = V A ( TA ) TB
1 1

VC = VB TC = 300

VD = V A TD = TC ( TA ) TB

T A = 450

H AB = 0;W AB = U AB = nCV (TB T A ) > 0 WBC = 0; H BC = U BC = nCV (TC TB ) < 0

2)

H CD = 0;WCD = U CD = nCV (TD TC ) = nCV WDA = 0; H DA = U DA = nCV (T A TD ) > 0

TC (T A TB ) < 0 TB

3) =

W AB + WCD T T = 1 B < 1 C H DA TA TA

4) let call SBC and IBC the entropy variation and Clausius integral respectively, we recall that in C H , T is the temperature of the source which heat is exchanged with, i.e. T = TC. I BC T B ,unrev Therefore:
C nCV nC dT = V (TC TB ) TC TC B,unrev TC B ,unrev 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 T H dT S BC = nCV = nCV ln( C ) T T TB B , rev B , rev C

I BC

and it is easily shown that: SBC > IBC. Analogous demonstration for DA:
A

I DA S DA

D ,unrev A

H H
T

A nCV nC = dT = V (T A TD ) TA T A D ,unrev TA

D , rev

= nCV

T dT = nCV ln( A ) T TD D , rev

and again : SDA > IDA. 3) U = 0 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) 2) 3) 4) 5) DATA: Draw the cycle in a (P,V) plane (V being the abscissa) 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 VC = 2 pC = TC = T A = 300

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 TB = 2T A = 600

2,3) V A = 1
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

WT = W AB WCA 0.076

5) U AB = nCV (TB T A ) = 5 nR T A 6.15[atm litre]

2

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 P A B

C V

DATA: n=1; CV= 3/2 R; PA = 1 [atm] ; VA=1 [litre] Exercise 6.8.5.

; VB = 1 [litre] ; VC = 1 [litre] ;

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 and 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) 2) cycle. 3) 4) The values of pressure, temperature and volume in each point A, B, C, D. The works WAB, WBC, WCD, WDA done by the gas in each branch AB, BC, CD, DA of the The exchange heat HAB, HBC, HCD, HAD, in each branch of a cycle. The efficiency of the cycle P A B

DATA: n=1; CV= 3/2 R; PA = 1 [atm] ; VA=1 [litre] V VB = 1 [litre] ; VC = 1 ; [litre] ; Solution

pA = 1
1) V A = 1

pB = p A VB = 1 TB = p A VB VB = TA nR VA

pC =

nRTC V B = pA VC VC VB TA VA

VC = 1 TC = TB =

p A VA nR V p D = pC = B p A VC TA =

VD =

V AVC VB

TD = T A

2) W AB = p A (VB V A ) = ...... > 0

WBC = nRTB ln( WCD =

VC V ) = p AVB ln( C ) VB VB

pCVC VV p V p V (V A VB ) = pC ( A C VC ) = C C (V A VB ) = B B (V A VB ) = p A (V A VB ) = W AB VB VB VB VB VA V ) = p AV A ln( B ) VD VC

WDA = nRTA ln(

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 . 4) 5) 6) 7) 8) Draw the 3 thermodynamic transformations AB, BC, CD in the plane PT (P ordinate and T abscissa) The total transformation ABCD is cyclic? Why? Write the values of the volume, pressure and temperature in each point A, B, C, D . Find the works WAB, WBC, WCD done by the gas in each branch AB, BC, CD of the transformation. Find the total variation UAD of the internal energy from A to D 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
3) V A = 1

pB = p A TB = 400 VB = nR TB TB = PA PB TA
VB = 1,33

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

TA =

p A VA = 300[ K ] nR

pD = 1 TD = T A = 400 VD = 3,958

W AB = p A (VB V A ) = 0,9846 V 4) WBC = nRTB ln( C ) = 4,2656 VB WCD = pC (VD 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 .

9)

Draw the 3 thermodynamic transformations AB, BC, CD in the plane VT (V ordinate and T abscissa) 10) Is the total transformation ABCD cyclic? Why? 11) Write the values of the volume, pressure and temperature in each point A, B, C, D . 12) Find the works WAB, WBC, WCD done by the gas in each branch AB, BC, CD of the transformation. 13) 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
VB ) = 2,047 VA VD ) = 2,729 VC

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 = nRTA ln(
4) W BC = 0

WCD = nRTC ln(

5) U AD = n Cv (TD TA ) = 12,305

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 TD= 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 UAB and the exchanged heat QAB in the transformation AB c) The work LBC performed by the gas, the variation of internal energy UBC and the exchanged heat QBC in the transformation BC d) The work LCD performed by the gas, the variation of internal energy UCD 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 V A B C D L AB BC CD DA 0 nRTB ln(VC/ VB) 0 nRTA ln(VB/ VC) 2 litre 2 litre 4 litre 4 litre U nCv(TB-TA) 0 nCv(TA-TB) 0 T 300 K 100 K 100 K 300 K Q =UAB=12atm litre =LAB=4ln(2) atm litre =UCD=-12atm litre =LAB=-12ln(2) atm litre P 6 2 1 3 atm atm atm atm