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d(nU) = dQ + dW …….

first law for closed system


d(nU) = dQrev + dWrev……..reversible process
= Td(nS) – Pd(nV)
d(nU) = Td(nS) – Pd(nV)
Any process, closed system, 1 equation stage to other.

→H = U + PV
nH = nU + P(nV)
d(nH) = d(nU) + Pd(nV) + (nV)dP
d(nH) = Td(nS) – Pd(nV) + Pd(nV) + (nV)dP
d(nH) = Td(nS) + (nV)dP

→ A = U – TS
A = U – TS
nA = nV – TnS
d(nA) = d(nU) – (dT)nS – Td(nS)
d(nA) = Td(nS) – Pd(nV) – Td(nS) – (nS)dT
d(nA) =- Pd(nV) –(nS)dT

→ G = H – TS
nG = nH – T(nS)
d(nG) = d(nH) –Td(nS) – (nS)dT
= Td(nS) + (nV)dP – Td(nS) – (nS)dT
d(nG) = (nV)dP – (nS)dT

1) H = U + PV
G = H – TS
“Maximum amount of non-expensive work for isothermal or isobaric process”.
A = U – TS
Where A is Helmetz free energy
“Maximum work obtainable from an isothermal process”.
2) F = F(x,y)

3) For any closed system and change occurring between two equations of states we can
write,
d(nU) = Td(nS) – Pd(nV) where U,S,V are molar properties
For, closed system
Change occur between equation of states
H = U + PV
nH = nU + P(nV)
on differentiation, d(nH) = d(nU) + Pd(nV) + nVdP
d(nH) = Td(nS) – Pd(nV) + Pd(nV) + nVdP
d(nH) = Td(nS) + nVdP
Similarly,
d(nA) = d(nU) – Td(nS) – nSdT
d(nA) = Td(nS) – Td(nS) – nSdT- Pd(nV)
d(nA) = - Pd(nV) – (nS)dT
And,
d(nG) = d(nH) – Td(nS) –(nS)dT
= Td(nS) + (nV)dP – Td(nS) – (nS)dT
d(nG) = (nV)dP – (nS)dT
Four fundamental property relations for homogeneous fluid at constant composition, for
one mole,
dU = TdS –PdV
dH = TdS + VdP
dA = - PdV – SdT
dG = VdP – SdT

Maxwell’s Equations:
It helps in replacing unmeasurable quantities appearing in equations by measureable quantities.
Each Maxwell’s equation are derived from exact differential equations of the four energy
properties.
Deriving Maxwell’s equation
1) dU = TdS – PdV

and (

Now, and

But,

dF = Mdx + Ndy

M = T, x = S, N = -P, y = V
2) dH = TdS + VdP
and (

and

M = T, x = S, N = V, y = P

3) dA = -PdV – SdT
dF = Mdx + Ndy

F = A, M = -P, V = x, N = -S, T = y

4) dG = VdP – SdT

F = A, M = V, x = P, N = -S, y =T

Maxwell’s Relations are,


Deriving certain relationship for enthalpy and entropy as a function of T and P

H = H (T,P)

We should find out and

We know that, (definition of heat capacity)

Moreover, dH = TdS +VdP

dH/dT = T dS/dT + V dP/Dt


Now, we know that,
dH = TdS + VdP

At constant temperature,

But,

Maxwell’s relationship

So,

……………..equ.A
Now, for entropy S = S(T,P)

We know that dH = TdS + VdP

At constant P,
But, we know that

And we know that


……………………………equ.B
From equation A,
dF = Mdx + Ndy

Now M =Cp, x = T, N =

Internal energy as a function of T and V


U =f(T,V)

We know that dU = TdS – PdV


At constant x, dV = 0
Dividing the equation with dT we get

At constant V, dV = 0
But,

We know that dV/V = βdT = KdP = 0


S = S(T,V)

But we know that dU = TdS – PdV

dV/dT = T dS/dT –P dV/dT


At constant V,
But,

Let V = f(P,T)

At constant V, dV = 0

So,
and

Prove that,
T = f(P,V)

Substituting in the equation we get,

Relationship between Cp and Cv

We know that,

and
Therefore,

(
Substituting in ongoing equation will give,

Prove that,

We know that, S = f(P,T)

But,

……..at constant S,

Joule Thomson coefficient

Now, H = f(P,T)

At constant H, dH = 0

Now, we know that dH = TdS + VdP

= Joule Thomson coefficient

But,

…………………equ.2

From equ.1, we have


Substituting in equ.1, we get,

Effect of temperature, pressure and volume on U,H and S.


Most useful relation are those giving the effect of T and P on S and H.
We know that,
……….equ.1

and ………equ.2
We know that,

At constant volume,
dU = CvdT

and

Similarly,
…………………..equ.5
and ……….equ.6

Method of calculation of entropy and enthalpy of a fluid in a given thermodynamic state


using equation 1, 2, 5 and 6 is explained below,

It is assumed that following data is available with us,


1) PVT relationship either as an EOS or tabular
2) Heat capacity at P = P0 and T = T0
3) Enthalpy H0 and entropy S0 at T = T0 and P = P0
Assume properties to be calculated at Temperature, T and Pressure P at point B in diagram,
Evaluation of any property as a function of temperature and pressure.
S0 and H0 are represented by point A.
Since S and H are state functions ∆S and ∆H for the fluid will be the same when it undergoes a
change of state from state A to state B, as ∆S and ∆H calculated for any process occurring
between states A and B
We can therefore device a two step process for bringing about this change.
Process I : constant pressure heating from T0 to T (AC)
Process II: constant temperature compression P0 to P (CB)
Step 1: Let H’ and S’, are enthalpy and entropy at point C.
So, ∆H = H’ – H0 = ……………………..from equ.5
And, ∆S = S’ – S0 = ……………equ.2
Since S0 and H0 are known H’ and S’ can be evaluated.
Step 2: ∆H = H – H’ =………………from eqn.6
∆S = S – S’ = ……………………..equ.1
Knowing H’ and S’ from step-1 we can find H and S in step 2.
The integrals are evaluated using PVT data.
If data is available I te form of EOS derivative is obtained by differentiation and the integration
is obtained analytically.
If the data is available in tabular form,
Calculate the internal energy, enthalpy, entropy and free energy for one mole of N2 at 500˚C and
50 bar assuming that N2 behave as an ideal gas. The molal heat capacity of N2 is given as,
Cp = 27.3 + 4.2*10-3T, T in ˚K and Cp as J/mol˚K
Enthaply of N2 is zero at 273K and 1 bar. The entropy of N2 is 192.4 J/molK at 298K and 1 bar.
Solution:
Assuming that N2 is initially at 273K and 1 bar for evaluation of enthalpy.
And at 298 K and 1 bar for evaluation of entropy.
Forst a constant pressure process at 1 bar upto 773 and then constant temp process at 773 K to 50
bar.
Step-I:
∆H = =
= 14.748 * 10-3 J/mol
∆S = =
∆S = 28.02 J/mol K
Let H’ and S’ be the enthalpy and entropy at the end of step 1 than,
H’ = H0 + ∆H = 0 + 14.748 * 10-3 = 14.748 * 10-3 J/molK
S’ = S0 + ∆S = 192.4 + 28.02 = 220.42 J/molK
Step 2:
∆H = and
Given that N2 is an ideal gas,
So, PV = RT → V = RT / P

So, ∆H =
∆H = 0 (because, RT/P = V)
∆S =
= 8.314 ln50/1
= 8.314 * ln50
=_______J/molK
H = H’ + ∆H = 0 + 14.748 * 103
H = 14.748 * 103 J/mol
S = S’ + ∆S = 220.42 J/molK
Internal energy U = H – PV
= H – RT
= [14.748 * 103] – [ 8.314 * 773]
U = 8.321 * 103 J/mol
Gibb’s free energy, G = H – TS
= (14.748 * 103) (773* )
3
= *10 J/mol
Residual Property, Departure Function
MR = M – Mig
M = Actual property
Mig = ideal gas property
But, rough estimate can be made using residual property.
It is the difference between the thermodynamic property at the specified temperature and
pressure and the property that the substance would have exhibited at the same temperature and
pressure, had it been ideal gas.
If we apply it to enthalpy and entropy, and denoting ideal gas with “ig”.
HR = H – Hig……………….equ.1
SR = S – Sig…………………equ.2
HR and SR are know as, enthalpy departure and entropy departure functions, respectively. Since,
gas can’t be both real and ideal at a given T and P, they are each termed as hypothetical
properties or hypothetical ideal gas state.
→If we partially differentiate equ.1 and equ.2 wrt pressure,
…………………equ.3
…………………..equ.4
We know that, …………………………….equ.5
dH = Tds + VdP

………..equ.6

For ideal gas,


PV = RT → V = RT/P


→ ……..equ.7

…………equ.8

The ideal gas behavior is characterized by


PV = ZRT, where z = Compressibility factor

Then, V = ZRT/P
………..equ.9

Substitute equ. 9 in equ 5 and equ.6 we get,

………equ.10

= (i.e. V = ZRT/P)

……………equ.11

Substituting equ’s, 7,8,10 and 11 in equ’s 3 and 4 we get,

…………equ.12

……….equ.13

Integrated within the pressure P0 and P we get,

∆HR = …………equ.14

And, If P0 = 0, ∆HR = HR and HR0 = 0 (i.e. ideal gas)

∆SR = ………equ.15

And are evaluated using experimental PVT data, and the integrals or graphical methods.
Analytical information is possible when Z is expressed as EOS or generalized
correlations.
If we, use reduced P and reduced T equ.14 and 15 will be converted as shown below,

Pr = P/Pc, Tr = T/Tc, dP = PcdPr, dT = TcdTr

∆HR =

………..equ.16
Similarly, we can get,

∆SR/R = ……………..equ.17

Z and required can be obtained from the centralized compressibility charts. Thus we can
evaluate ∆SR and ∆HR.
If we know the value of S and HR and reference pressure P0 (which we can fix
R

arbitrarily) we can find out H and S using the definition of residual properties.
Let’s say, at P = P0 , = 0 and = 0. Then equ.16 and 17 will give the values of SR and HR

Using HR = H + Hig and SR = S – Sig

We get, H = HR + Hig and S = SR + Sig

→ We know that

Using,

We get,

d(nG) = (nV)dP – (nS)dT


→ d(nG) = 0
N is constant, dG = 0
→GV = GL…………at equilibrium

dGα = dGβ
VαdPsat – SαdT = VβdPsat – SβdT
dPsat/dT = (Sβ – Sα)/ (Vβ – Vα) = ∆Sαβ/∆Vαβ