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Adiabatic path
Adiabatic path is the one where the state of the system
changes without loss of heat to surrounding. According
to 1st law E=q+W, for adiabatic process q=0. For small
reversible change in volume, the system will perform
work on the surrounding and the change in the
temperature of the system is given by:
dV
V
T
dT
dV
V
V
CV
R
CV ln 2 R ln 2 R ln 1
T
V
V1
V2
T1
CV dT pext .dV RT
Carnot Cycle
Carnot cycle considers following cyclic path for an engine
following a reversible paths.
Gas at
P2,V2,T1
Isothermal
expansion
Ideal Gas
T1,P1,V1
Adiabatic
Compression
Adiabatic
expansion
Isothermal Compression
Gas at
P4,V4,T2
Gas
P3,V3,T2
Adiabatic path
I
2
4
3
Isothermal Path
V1
E 0 q w1 q1 P.dV q1 RT1 ln
V3
E 0 q w3 q3 P.dV q3 RT2 ln
RT2 ln
V1
V3
V
V
w1 w2 w3 w4 RT1 ln 2 RT2 ln 4
V1
V3
qTotal q1 q 2 q3 q 4 RT1 ln
wTotal
qTotal wTotal
or
ETotal 0
Carnots Insight
In a feat of insight Carnot realized that although q
depends on the path taken, the ratio qrev/T does not! He
called this new term entropy, a state variable. Let us try
to calculate this term as we travel along the Carnot
cycle. Clearly for paths II and IV it is zero since for any
dq
T1
T1
T1
V2
V1
RT1 ln
T1
V2
V1
R ln
Path III :
dq
1
T2
T2
q3
dq T
V4
V3
RT2 ln
T2
V4
V3
R ln
q1 q3
T1 T3
V2V4
V2
V1
T
T
CV ln 1 CV ln 1 0
R ln
R ln
V4
T2
T2
V1V3
V3
R ln
w q1 q3
q
T
1 3 1 2
q1
q1
q1
T1
sin ce
q1 q3
0
T1 T2
2V
RT ln 2
V
w RT ln
q
R ln 2 Entropy change for system
T
q
S surrounding
R ln 2 Entropy change for surroundin g
T
STotal 0
S system
q E w
0
T
T
T
T
T
T1
T
C dT
dT
dq
S
P
CP
C P ln 2 isobaric path
T
T
T
T1
Stran
H Tr
TTr
T
dT H m
dT
S (T ) S (0 K ) C P ( s )
C P (l )
T
Tm
T
o
TM
0
dq rev dw P.dV
T
T
T
E 0
d ( PV ) 0 PdV VdP dV
V
dP
P
V .dP
dP
nR
T
P
P
S nR ln 2
P1
dS
Entropy of Mixing
Consider two non-reacting gases A and B initially at identical
pressure, P separated from each other. If we allow them to
mix they will do so spontaneously and it is difficult to separate
them. The mixture will have identical pressure P, but we can
think of it as if its made up sum of partial pressures of A and
B. We can calculate the net change in the entropy of this
system.
X AP
X P
n A R ln( X A ) S B nB R ln B nB R ln( X B )
P
P
This
ST R.(n A nB ) X A ln( X A ) X B ln( X B )
S A n A R ln
is a