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