Scribd
Upload
74 views

Thermodynamics Lecture 20 Gibbs

This document discusses Gibbs free energies and the Gibbs-Duhem equation. It defines total, molar, and partial molar Gibbs free energies. The Gibbs-Duhem equation relates how the activity of one component varies with composition based on how the activities of other components vary. This allows determining partial molar free energies and activities from integral molar free energies of mixing using tangential intercepts. The document also discusses applying these concepts to regular solutions and relating excess free energy of mixing to activity coefficients. Finally, it shows how vapor pressure over a solution can relate to the activity of a component in the solution.

Uploaded by

sabavoon
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
74 views

Thermodynamics Lecture 20 Gibbs

This document discusses Gibbs free energies and the Gibbs-Duhem equation. It defines total, molar, and partial molar Gibbs free energies. The Gibbs-Duhem equation relates how the activity of one component varies with composition based on how the activities of other components vary. This allows determining partial molar free energies and activities from integral molar free energies of mixing using tangential intercepts. The document also discusses applying these concepts to regular solutions and relating excess free energy of mixing to activity coefficients. Finally, it shows how vapor pressure over a solution can relate to the activity of a component in the solution.

Uploaded by

sabavoon
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 2

Thermodynamics Lecture 20 Gibbs-Duhem Equation and activity coefficients in

Regular Solutions

There are really three kinds of Gibbs Free Energies that we are considering

G’ = Total Gibbs Free Energy in the system (in Joules)


G = Molar Gibbs Free Energy in the system (Joules/mole). We have talked about integral
molar Gibbs Free Energies of mixing, that is the Gibbs Free Energy change to make one
mole of a solution. We can also define the Gibbs Free Energy change associated with
one mole of a particular species
GA = (dG’/dnA)T,P, nB = the partial molar Gibbs Free Energy of A = GA0 + GMA,= GA0 +
RTlnaA = The Gibbs Free Energy associated with one mole of A dissolved in the
solution.

On a differential scale
(1) dG’ = GA dnA + GB dnB + GC dnC + …
On a macroscopic scale
(2) G’ = GA nA + GB nB + GC nC + …
If we differentiate (2), we get
(3) dG’ = GA dnA + nA d GA +GB dnB +nB dGB +GC dnC + nC d GC +…
If we subtract (1) from (3), we get the Gibbs-Duhem equation
(4) 0= nA d GA + nB dGB + nC d GC +...
(5) Or 0 = nA RTdlnaA + nB RTdlnaB + nC RTdlnaC +...
This is the Gibbs-Duhem equation. It allows us to predict how the activity of one
component varies with composition if we know how the activities of the other
components vary with composition.
Putting this in terms of molar Gibbs Free Energy in a binary solution:
G= G’/ni = XA GA + XB GB
On a differential basis, considering the Gibbs-Duhem equation
dG = GA d XA + GBd XB Because XA = 1-XB, then dXA = -dXB, so
dG = (GA - GB) dXA and dG/dXA = (GA - GB)
We can use this to get partial molar Gibbs Free Energies of mixing for A and B
(GA and GB) from G as a function of composition (XA and XB )
This is especially useful for getting partial molar free energies of mixing from
integral molar free energies of mixing.
First multiply the derivative expression by XB,
XBdGM/dXA = XBGMA - XBGMB Then add GM as a function of composition
+ GM = XA GMA + XB GMB
GM + XBdGM/dXA = XBGMA - XBGMB +XA GMA + XB GMB = GMA =
RTlnaA
Similarly, GMB = GM + XAdGM/dXB = RTlnaB
We can get partial molar free energies and activities from GM versus composition by the
method of tangential intercepts (See Figure 9.5, p 220)

To apply this to regular solutions, let’s define one more type of Gibbs Free Energy of
Mixing
Gmix = Hmix - TSmix = Xi RTlnai = Xi RTlni + Xi RTlnXi because ai = i Xi .
We can separate the ideal and non-ideal parts of the free energy of mixing, since we
know that if the mixing was ideal, then
Gmix ideal = - TSmix = Xi RTlnXi Then we can say
Gmix = Gmix xs + Gmix ideal = Xi RTlni + Xi RTlnXi
Gmix xs = Xi RTlni accounts for all of the non-ideal effects of the mixing, and we can
relate the excess free energy of mixing to the activity coefficients of the components in
the mixture. For a regular solution, because the entropy of mixing is ideal,
Gmix xs = Hmix =  XA XB
Then we can obtain the activity coefficient from the excess free energy of mixing by the
tangential intercept method.
GxsA = RTlnA = Gxs + XBdGxs/dXA
dGxs/dXA = d( XA XB)/ dXA =  (XB dXA /dXA+ XA dXB/dXA) =  (XB-XA)

GxsA =  XA XB + XB (XB-XA) =  XB2 = RTlnA


Similarly  XA2 = RTlnB

From these we can find the activity coefficient of either A or B as a function of


composition from knowledge of  . Also note that this behavior fits the criteria that we
discussed earlier. That is as XB => 0, A => 1 approaching ideal behavior as we expect,
and as XB => 1, A => exp ( /RT) = Ao the Henry’s law coefficient.

An application of reactions involving species in solution.


Species that have high vapor pressures will also evaporate from solutions that contain
that specie. We can relate the vapor pressure of the specie over the solution to the
activity of the specie in the solution.
The chemical reaction can be written
A(in solution) = A(g)
G = GA (g) - GA (solution) = GAo (g) + RTlnPA - GAo (condensed) - RTlnaA

G = GAo (g)- GAo (condensed) + RTln(PA /aA) = Govap + RTln(PA /aA) = 0 at


equilibrium
Note that if we had pure A
Govap = GAo (g)- GAo (condensed) = - RTlnPAo where PAo is the vapor pressure of pure
A
Since these are both equal to -Govap.
RTln(PA /aA) = RTlnPAo and aA = PA /P Ao This gives us a way to measure the activity
of a component in a condensed solution. Note that if we know the composition of the
solution,
aA = PA /P Ao = A XA , so A = PA /(P Ao XA) We can determine the activity coefficient
as a function of composition.

You might also like

pFad - Phonifier reborn

Pfad - The Proxy pFad of © 2024 Garber Painting. All rights reserved.

Note: This service is not intended for secure transactions such as banking, social media, email, or purchasing. Use at your own risk. We assume no liability whatsoever for broken pages.


Alternative Proxies:

Alternative Proxy

pFad Proxy

pFad v3 Proxy

pFad v4 Proxy