Thermodynamics of Materials 3.

00 Fall 2001

Example Problems for Week 3

One mole of an ideal gas, in an initial state P = 10atm, V = 5L, is taken, reversibly, in a clockwise direction, around a circular path given by (V ; 10)2 +(P ; 10)2 = 25. Calculate the amount of work done by the gas as a result of this process, the change in internal energy of the gas, and the maximum and minimum temperatures attained by the gas during the cycle. How do these answers change if the number of moles of gas double for the same P-V cycle?

Example Problem 3.1

The internal energy is a state function and only depends on the initial and H nal states of the system. This is a closed integral so the change in internal energy is zero. dU = 0. There are two ways to calculate the work done by the system during the cycle. The R rst is to analytically integrate PdV , the second is to assess the area under the curve graphically. (P ; 10)2 + (V ; 10)2 = 25 is the equation of a circle in the P-V plane with center at (10 10) and radius 5. The initial state is at the lowest allowed volume for the system, (V0 P0).
P

Solution 3.1

10 =P_o =P_1

V_o

10

V_1

Figure 1: P-V diagram for the work cycle.

First we must nd P = P (V ) in order to perform the integration. P = 10 25 ; (V ; 10)2 where the plus sign corresponds to the upper half of the circle (P+(V )) and the minus sign corresponds to the lower half (P;(V )). Now let V 0 = V ; 10 in the following.

Ws =

Z V1 =5
0

V0 =;5
0

10 +

Ws =

Z V1 =15

V0 =5

P+(V )dV +
Z V0 =;5
0

Z V0 =5

Ws = PdV P;(V )dV

V1 =15

25 ; V 02 dV 0 +

V1 =5
0

10 ; 25 ; V 02dV 0

By this method the work done by the system is 25 101:3J = 7956J . The second method involves examining the area under the curve, a circle with radius 5. So the area is 25 L atm. This again is the work done by the system equal to 7956J . The maximum and minimum temperatures can be found from the ideal gas law for one mole of gas, PV = RT . Tmax attains when (PV ) is a maximum and Tmin attains when (PV ) is a minimum. Let P 0 = P ; 10 and V 0 = V ; 10 so PV is an extremal when P 0V 0 is extremal.

25 ( ; 8) = 25 L atm Ws = 25 ( + 8) + 2 2

q The extrema are for V 0 = 25 2 . Examination or checking the sign of the second derivative, d2 F > 0 for a minimum and d2 F < 0 for a maximum, gives the following. dV 2 dV 2

P 0V 0 = f (P 0(V 0) V 0) = 25 ; V 02 V 0 df = 0 = p25 ; V 02 V 0 1 p ;2V 0 dV 0 2 25 ; V 02 " 02 ; V 02 # 25 ; V p 0= 25 ; V 02

h] q V0 P0 Vq Pq q 25 25 25 max q2 10 + q 2 10 + q 25 2 q2 25 25 25 25 min ; 2 ; 2 10 ; 2 10 ; 2 This leads to Tmax = (PV )max=R = 2203K and Tmin = (PV )max=R = 502K . If the number of moles are doubled the work done by the system is still W = 7956J but the maximum and minimum temperatures are decreased by a factor of two from T = PV=(nR) and Tmax = 1102K and Tmin = 251K .

Example Problem 3.2

One mole of ideal gas at 25 C and 1atm undergoes the following reversible process:

1. Isothermal expansion to 0:5atm, followed by 2. Isobaric expansion to 100 C, followed by 3. Isothermal compression to 1atm, followed by 4. Isobaric compression to 25 C The system then undergoes the following cyclic process: 1. Isobaric expansion to 100 C, followed by 2. A decrease in pressure at constant volume to P atm, followed by 3. An isobaric compression at P atm to 24:5L, followed by 4. An increase in pressure at constant volume to 1atm.

Calculate the value of P which makes the work done on the gas in the rst cycle equal to the work done by the gas in the second cycle.

For one mole of an ideal gas PV = RT and W = PdV . W is the work done by the gas. There are 3 kinds of processes here and the work must be calculated accordingly. V1 = RT ln P0 . 1. For an isothermal process (T is constant): P = RT=V so W = RT ln V P1 0 2. For an isobaric process (P is constant): W = P (V1 ; V0 ) = R(T1 ; T0 ) 3. For a constant volume process (one of the isochoric processes) W = 0 but the pressure and temperature will change. Let's begin by summarizing the transformations of the gas by recording the T,P,V before and after each process in liters, atmospheres and Kelvin and also the form of the work done by the system.

Solution 3.2

T0 298 298 373 373 298 373 T3 . W=

P0 1 0:5 0:5 1 1 1 Pu Pu

V0 . . . . . Vu Vu 24:5

T1 298 373 373 298 373 T3 T4 .

P1 0:5 0:5 1 1 1 Pu Pu 1

V1 . . . . Vu Vu 24:5 24:5

Wi 0 W1 = RT ln P P1 W2 = R(T1 ; T0 ) 0 W3 = RT ln P P1 W4 = R(T1 ; T0 ) W10 = R(T1 ; T0 ) W20 = 0 0 W3 = R(T1 ; T0 ) W40 = 0

For the rst reversible process the work done by the system is W = P4 i=1 Wi .

Wi = 298R ln 2 + R(373 ; 298) + 373R ln 0:5 + R(298 ; 373) W = (298 ; 373)R ln 2 = ;75R ln 2
4 X
i=1

0 For the second cyclic process the work done by the system is W 0 = P4 i=1 Wi .

W0 =

Wi0 = R(373 ; 298) + 0 + R(T4 ; T3 ) + 0 W 0 = 75R + R(T4 ; T3 )

So we must nd the unknown temperatures using T = PV=R and V = RT=P . Pu 373R = 373P u V T3 = P u= u R R 1 24:5 T4 = PuR 24:5 ; 373Pu) = 75R + RPu ( 24:5 ; 373). Now W 0 = 75R + R( PuR R

The restriction that the work done on the gas in the rst cycle equals the work done by the gas in the second cycle is equivalent to ;W = W 0.

:5 ; 373) W + W 0 = 0 = ;75R ln 2 + 75R + RPu( 24 R 2 ; 1) Pu = 75(ln 24:5 ; 373 R J L atm 1atm 103 L In the above R = 8:314 moleK 5 1:01310 Pa m3 = 0:08207 moleK . So Pu = 0:3atm.