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1 Vander Waals equation of state for real gas a (V b) = RT V2 State variable P+ d(any state variable) = 0

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

The ideal gas equation P V = RT

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

Q T Few important points about entropy:

In this relation x and y are only independent variables. Example I: Taking x = P and y = V as

2 the independent variables. T P S V T V S P =1 T dS = CP dT T


P V

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

P dV + V dP = RdT CP CV = R 2) derive the relation: CP CV = T P T V T

From ideal gas equation P =T P T

T dS = CV dT + T Second T dS equations

P T

dV
V

CP CV = R PV CP CV = T From ideal gas equation P =T P T ,


V

V =T P T

T dS = dh V dP CP = h T , dh = CP dT
P

V T V T

CP CV = T 3) derive the relation: C P C V = T

From ideal gas equation 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

P2 +(CV +R) log P1 P2 P1 + CP log

S2 S1 = CV log

V T V T

P 2 P

P V P V

now replacing for V2 /V1 S2 S1 = CV log


T

CP CV = T

T2 T1

+ R log

T2 P1 T1 P2 P1 P2

4) derive the entropy relations: by using rst T dS equation T dS = dU + P dV dU = CV dT

S2 S1 = (CV + R) log S2 S1 = CP log T2 T1

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

As for reversible processes S T =0


rev

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 ( )

4 T G T = T U + PV T S T Canonical partition function Quantum partition function Z=


i

As for reversible processes S T T G T =0


rev

Classical partition function Q T2 Z= 1 h3n eE d

G T T 1 T T

( ) =Q ( )
1 V V T

Semi-classical partition function Z= 1 n! h3n eE d

Coecient of volume expansion =

Grand partition function Z=


n

en Zn

Isothermal compressibility K= 1 V V P

Partition function for a classical one dimensional harmonic oscillator


T

Bulk modulus of elasticity = K= 1 V 1 K V P

p2 + 2m 2 n2 q 2 2m

Classical canonical partition function is given by 1 eE d Z= h


T

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

5 quantum canonical partition function is given by Z= e i


i

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