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1) during an adiabatic and a reversible process entropy change is zero. 2) when a certain amount of heat is added to a system, its entropy increases. Maxwell thermodynamic potentials GPHSUVFT
e.g.
C
dP = 0
dG = V dP SdT dh = T dS + V dP dU = T dS P dV
dF = P dV SdT It is a gas for which 1) Internal energy is the function of tem- when the number of particles changes, perature only dG = V dP SdT + dN U = U (T ) dh = T dS + V dP + dN U U = 0, =0 dU = T dS P dV + dN V T P T dF = P dV SdT + dN 2) Specic heats CP and CV are independent of temperature. Maxwell thermodynamic relations By dierentiating the ideal gas equation partially with respect to V and P , respecP S V S = , = tively, we get the following relations: V T T V P T T P =T P T ,
V
V =T
V T
T P
=
S
V S
,
P
T V
=
S
P S
Entropy - an intensive state variable General derivation relation Clausius found that for a reversible process (T S P V ) energy-energy relation integration of the quantity Q/T is zero, i.e, T S T S Q =0 x y y x y x x T S2 S1 = dS = Q T = P x V y
x
P y
V x
In this relation x and y are only independent variables. Example I: Taking x = P and y = V as
V T
dP
P
Importance of T dS equations: from these equations we can derive all the other therExample II: Taking x = T and y = S as modynamic relations, in fact these are the the independent variables. heart of thermodynamics, Now I would like to derive few relations: P V P V = 1 1) derive the famous molar specic heat reT S S T S T T S lation CP CV = R, By equating rst and HUT relations: second T dS equations, we have h S V P CP = =T dV +T dP (CP CV )dT = T T P T P T V T P U S From ideal gas equation CV = =T T V T V P V P =T , V =T T T V T P J = P h (CP CV )dT = T (P dV + V dP ) First T dS equations
V P
T dS = dU + P dV CV = U T , dU = CV dT
V
T dS = CV dT + T Second T dS equations
P T
dV
V
V =T P T
T dS = dh V dP CP = h T , dh = CP dT
P
V T V T
V T
2 P
P V
3 CP CV = T x y y z P T V T now replacing for T2 /T1 in the above entropy relation S2 S1 = CV log S2 S1 = CV log = 1
T
z x
= 1
y
P2 V 2 P1 V 1
+ R log
V2 V1 V2 V1 V2 V1
now taking x = P, y = T, z = V P T P T T V =
V
V P
S2 S1 = CV log
V T V T
P 2 P
P V P V
CP CV = T
T2 T1
+ R log
T2 P1 T1 P2 P1 P2
T2 + R log T1 + R log P1 P2
Helmholtz relations I: F = U T S, T F T = T F U = S T T U T S T
T dS = CV dT + P dV dS = CV dS = CV dS = CV S2 S1 = CV log dT P + dV T T dT P + dV T T R P = T V 1 dT + R T T2 T1
1 dV V V2 V1
F T
U T2
+ R log
Now from the ideal gas equation, we can write two more expressions for change in Helmholtz relations II: entropy: P1 V1 P2 V2 G U PV = G = U T S + P V, = S+ T1 T2 T T T
F T T 1 T T
( ) =U ( )
G T T 1 T T
( ) =Q ( )
1 V V T
en Zn
Isothermal compressibility K= 1 V V P
p2 + 2m 2 n2 q 2 2m
Partition function for a single atom of a mean energy mono-atomic ideal gas Z= V (2mkT )3/2 h3
Z=
kT h (log Z ) T
E = kT 2
E = kT If the energy is determined by the classical methods then we use classical partition Partition function for a quantum one function and when the energy of the system dimensional harmonic oscillator is derived with quantum methods then we use quantum partition function e.g. har1 = n + h n monic oscillator. 2
Z=
n
1
e (n+ 2 )h enh
n
Z = e 2 h
1 = 1 + x + x2 ... = 1x Z = e 2 h
1
xn
n
mean energy E =
1 1 eh
(log Z ) 1 1 E = h + h 2 e 1 Vibrational partition function for a diatomic molecule as a diatomic gas molecule possesses only one degree of freedom for vibration, we can regard it as one dimensional harmonic oscillator, 1 1 Z = e 2 h 1 eh 1 1 E = h + h 2 e 1 if there were n diatomic molecules n 1 1 h 2 Z= e 1 eh 1 1 h + h 2 e 1 Statistical denition of entropy approximate and exact E =n S = k log exact S = k Pi log Pi