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Solution Thermodynamics: Theory: Fundamental Property Relation

This document discusses fundamental property relations in thermodynamics. It introduces the Gibbs equation that relates changes in internal energy to temperature, entropy, and pressure. The Gibbs energy and enthalpy equations are also presented. The fundamental property relation for single phase systems is derived, relating the total Gibbs energy to temperature, pressure, and chemical potentials. This relation provides a generating function to calculate other thermodynamic properties through differentiation and algebra.

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Lim Ying Pei
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497 views

Solution Thermodynamics: Theory: Fundamental Property Relation

This document discusses fundamental property relations in thermodynamics. It introduces the Gibbs equation that relates changes in internal energy to temperature, entropy, and pressure. The Gibbs energy and enthalpy equations are also presented. The fundamental property relation for single phase systems is derived, relating the total Gibbs energy to temperature, pressure, and chemical potentials. This relation provides a generating function to calculate other thermodynamic properties through differentiation and algebra.

Uploaded by

Lim Ying Pei
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
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SOLUTION

THERMODYNAMICS:
THEORY

FUNDAMENTAL
PROPERTY RELATION

By : Dr Lim Ying Pei (UiTM Shah Alam)


FUNDAMENTAL PROPERTY RELATION
 The first Tds relation or Gibbs equation:

d  nU   Td  nS   Pd  nV  (6.1)
 Gibbs energy:
G  H  TS
(6.3)
 Multiplied by n and differentiated eq. (6.3):
d  nG   d  nH   Td  nS    nS  dT (6.3a)
 Enthalpy:
H  U  PV (2.11)
 Multiplied by n, differentiated and combined with eq. (6.1):
d  nH   Td  nS    nV  dP (6.4)
 Combine eq. (6.3a) and (6.4) to yield:

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d  nG    nV  dP   nS  dT (6.6)
 Equation (6.6) relates the total Gibbs energy of any closed
system to temperature and pressure.
 An appropriate application is to a single phase fluid in a
closed system wherein no chemical reactions occur. For
such a system the composition is necessarily constant, and
therefore
   nG      nG  
   nV and    nS
 P  T ,n  T  P ,n (A)

The subscript n indicates that the numbers of moles of all


chemical species are held constant.
 For more general case of a single phase, open system,
material may pass into and out of the system, and nG
becomes a function of the numbers of moles of the
nG  g  P , T , n1 , n2 ,..., ni ,... 
chemical species present, and still a function of T and P.

where ni is the number of moles of species i.


3
• Total differential of nG is
   nG      nG    nG 
d  nG     dP    dT     dni (B)
 P  T ,n  T  P ,n i  n i  P ,T ,nj

The summation is over all species present, and subscript nj


indicates that all mole numbers except the ith are held constant.
 The derivative in the final term is called the chemical potential of
species i in the mixture. It is define as

   nG  
i    (11.1)
  ni  P ,T ,nj
 With this definition and with the first two partial derivatives [eqn.
(A)] replaced by (nV) and –(nS), the preceding equation [eqn.
(B)] becomes
d  nG    nV  dP   nS  dT   i dni
i (11.2)
 Equation (11.2) is the fundamental property relation for single
phase fluid systems of variable mass and composition.

4
 For special case of one mole of solution, n = 1 and ni = xi:
dG  VdP  SdT   i dx i
i
(11.3)
 This equation relates molar Gibbs energy to T, P and {xi}.
G  G  P ,T , x1 , x2 ,..., xi ,...

 For special case of a constant composition solution:


dG  VdP  SdT (6.10)
 Although the mole numbers ni of eq. (11.2) are
independent variables, the mole fractions xi in eq. (11.3)
are not, because ixi = 1. Eq. (11.3) does imply
 G   G 
V   S    T  (11.5)
 P T , x (11.4)   P ,x

 Other solution properties come from definitions; e.g., the


enthalpy, from H = G + TS. Thus, by eq. (11.5),
 G 
H  G T  
 T  P , x
5
6

When the Gibbs energy is expressed as a function of its


canonical variables (T, P and {xi}), it plays the role of a
generating function, providing the means for calculation
of all other thermodynamic properties by simple
mathematical operations (differentiation and elementary
algebra), and implicitly represents complete property
information.

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