SCGL602306 / SCGF603636

Solutions & multicomponent systems

DNS - 2018 Thermodynamic

 SCGL602306 / SCGF603636

White, Chapter 3

So far our geochemical toolbox are filled with

• Enthalpy, entropy, Gibbs free energy.

Now, we will add more tools to our geochemical

toolbox…
• Phase equilibria, solutions & ideal solution
• Just for review: chemical potential, electrolyte solutions
& equilibrium, redox in aqueous solution

DNS - 2018 Thermodynamic

 SCGL602306 / SCGF603636

White, Chapter 3

Glossary & terminology

• Phase: part of parts of a system occupying a specific
volume and having uniform physical & chemical
characteristics. (E.g. sugar that wont dissolve in your ice tea)
• Species: a chemical entity, generally an element or
compound. (e.g. H2O, H2CO3, HCO3-)
• Component: basic chemical constituents of a system, of
which the various phases are composed. (e.g. in olivine, Mg,
Fe, Si, O)

DNS - 2018 Thermodynamic

 SCGL602306 / SCGF603636

White, Chapter 3

Glossary & terminology

• Degrees of freedom: equal to the sum of the number of
independent intensive variables and concentrations of
components in phases that must be stated.
• The Gibbs phase rule: rules to determine the degrees of
freedom (or variance) of a system at equilibrium.
• Solutions: homogenous phases produced by dissolving
one or more substances in another substance.

DNS - 2018 Thermodynamic

 SCGL602306 / SCGF603636

White, Chapter 3

Component
• Rule to determine the minimum number of components
in the systems.
! =#−%
• Where as,
• n = number of species
• r = number of independent chemical reactions possible between these
species

DNS - 2018 Thermodynamic

 SCGL602306 / SCGF603636

White, Chapter 3

The Gibbs phase rules

• Rule to determine the minimum
number of components in the
systems.

" =$−!+2
• Where as,
• f = degrees of freedom
• c = number of components
Determine the value of f, c and
• ! = number of phases ! for each point based on the
P-T phase diagram above.

DNS - 2018 Thermodynamic

 SCGL602306 / SCGF603636

White, Chapter 3

Solutions
• Compositions are expressed as Xi
• Total number of fractions should add up to 1.
• Example:
• Salad dressing (oil & vinegar) is not a solution
• If we mix fine powder of anorthite and albite, the result is not
plagioclase solid solution.
• But if we heat the anorthite-albite mixture to a sufficiently high
temperature that the kinetic barrier is overcome, resulting in atom
reordering thus we create solution.

DNS - 2018 Thermodynamic

 SCGL602306 / SCGF603636

White, Chapter 3

Solutions
%
• Raoult’s Law !" = $" !"
• Holds only for ideal solutions.
• Partial pressure are proportional to their mole fraction.

!" = ℎ. $" )*+ $" ≪ 1

• Henry’s Law
• Partial pressure is not equal to the mole fractions * vapor pressure of
the pure substance.
• They are varied linearly with X; thus deriving Henry’s Law
• H is Henry’s Law constant

DNS - 2018 Thermodynamic

 SCGL602306 / SCGF603636

White, Chapter 3

Ideal & Real Solutions

• Chemical Potential (μ): tells us how the Gibbs free energy
will vary with the number of moles, where number of moles,
component, temperature, pressure are constant.
• Ideal solutions:
• the interactions between different kinds of molecules in an ideal solution are
the same as those between the same kinds of molecules.
)
!","$%&' = !" + +, ln /"

DNS - 2018 Thermodynamic

 SCGL602306 / SCGF603636

White, Chapter 3

Fugacity
• Fugacities is created to compensate when we make
reference to gasses in dealing with real solutions but
doesn’t follow either Henry’s Law or Raoult’s Law.
• For an ideal gas, fugacity is identical to partial pressure.
• Fugacities are used to define another thermodynamic
parameter, activity.

$ *" *" $
!" = !" + &'() $ +≡ $ !" = !" + &' ln +"
*" *"

DNS - 2018 Thermodynamic

 SCGL602306 / SCGF603636

White, Chapter 3

FYI…
• Electrolyte Solutions
• Solutions in which the solutes dissociates to form ions which can
facilitate electric conduction. (Example: sea water)
• Equilibrium Constants
• The law of mass action, Le Chatelier’s principle, van Hoff relationship
• Redox in aqueous solutions
• Hydrogen cell potential
• pε – pH diagram, Eh – pH diagram (more on that in sedimentation &
sedimentary discussion)
• In magmatic systems

DNS - 2018 Thermodynamic