September 6, 2001
Reading: Chapter Three
Homework: 3.1,3.2,3.4,3.5,3.6
Heat Engines: A device converting heat into work.
First steam engine was built in 1769.
First thermodynamics analysis was done by Sadi Carnot in 1824.
q2
Heat reservoir at high
temperature T2
q1
Heat
engin
Heat reservoir at low
temperature T1
Work, w
Efficiency =
work obtained
w
=
heat input
q in
Carnot Cycle:
P
q2
T2
D T
1
q1
C
V
AB: Isothermal, reversible expansion (T2)
BC: Adiabatic, reversible expansion
CD: Isothermal, reversible compression (T1 < T2)
DA: Adiabatic, reversible compression
VB
VA
BC: adiabatic, q = 0, w2 = U = CV (T1 T2 ) = CV (T2 T1 ) > 0, (T2 > T1 )
AB: isothermal, U = 0, w1 = q 2 = RT2 ln
CD: isothermal, U = 0, w3 = q1 = RT1 ln
VD
VC
DA: adiabatic, q = 0, w4 = U = CV (T2 T1 ) = CV (T1 T2 ) < 0
Net work done = w = w1 + w2 + w3 + w4 = area enclosed by the cycle.
On a P-V diagram, the area enclosed by the cycle is the work done. Work done by
the system = area enclosed (clockwise); work done on the system = area enclosed
(counterclockwise).
w = RT2 ln
V
VB
+ RT1 ln C + CV (T2 T1 ) + CV (T1 T2 )
VA
VD
V
VB
+ RT1 ln C
VD
VA
In the two isothermal process:
w = T2 ln
PAV A = PBVB ;
PBVB = PC VC ;
In the two adiabatic process:
PCVC = PDVD .
PC VC = PBVB = PAV AVB
PDVD = PC VC VD 1 = PAV A
(1)
(2)
PC VC
PV V
(1)
=
= A A B
1
(2) PC VC VD
PAV A
VC
VD
So,
V
= B
VA
, i.e.,
VC VB
=
VD V A
Thus, the work done in one cycle is
w = RT2 ln
V
V
V
V
VB
+ RT1 ln C = RT2 ln B + RT1 ln B = R(T2 T1 ) ln B
VA
VD
VA
VA
VA
Heat input is
VB
VA
V
V
= q3 = RT1 ln C = RT1 ln B
VD
VA
qin = q 2 = RT2 ln
Heat output is q out
Efficiency, =
T
w qin q out T2 T1
=
=
= 1 1
qin
qin
T2
T2
PDV D = PAV A .
Now lets examine the entropy changes along the cycle.
q rev q rev
V
=
= R ln B
T
T2
VA
q
BC:
S 2 = rev = 0
T
q
q
V
V
CD: S 3 = rev = rev = R ln D = R ln B
T
T1
VC
VA
q
DA: S 4 = rev = 0
T
So, the change of entropy in the cyclic process is zero.
AB:
S1 =
The combined statement of the first and the second laws of thermodynamics:
The first law:
dU = q w
If the process is conducted reversibly, the second law:
q
q rev = TdS ; and w = PdV
dS = rev , i.e.,
T
So,
dU = TdS PdV
Since U, T ,P, and V are all state functions. The above equations is in fact
applicable whether or not the process is reversible.
If the process is conducted irreversibly, then
q
dS =
+ dS irr ,
i.e.,
q = TdS TdS irr .
T
dU = q w = TdS TdS irr w
.
And
dU = TdS PdV + {TdS irr w + PdV }
Hence we must have {TdS irr w + PdV } = 0 , although dS irr 0 and
PdV w 0 . It simply says that work (PdV-w) is degraded into heat (TdSirr).
U
U
dU =
U=U(S,V).
dS +
dV ;
S V
V S
U
U
Then, temperature is defined as T =
, and pressure as P =
.
S V
V S
We can write
If we choose U and V as independent variables and S as dependent variable,
S
S
then,
dS =
dU +
dV .
U V
V U
P
P
1
S
Since dS = dU + dV , then
= .
T
T
V U T