Ch.

11 Mixing Processes

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Ch. 11 Mixing Processes

11.1 Property Changes of Mixing

Mixing at constant T and P

The total volume change of mixing V is measured

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The total heat transfer Q (the total enthalpy change of mixing) is measured

H is usually called the heat of mixing (= HE )

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Property changes of mixing is defined as

CHANGE OF MIXING = REAL – ∑ (MOLE FRACTION  PURE PROPERTY)

V, H can be measured experimentally.

For ideal solution, Vid = 0 , Hid = 0

However,

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Excess Property

EXCESS = REAL – IDEAL SOLUTION

For ideal solution, GE = SE = VE = HE = 0

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Excess properties and property changes of mixing are related by

EXCESS property = property CHANGE OF MIXING

EXCESS property = property CHANGE OF MIXING

Property change of mixing is directly related to experiment, and was introduced historically prior to

excess property.

Excess property has more theoretical meaning.

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Example 11.1

Alternatively,

Results should be the same

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11.2 Heat effects of mixing processes

The heat of mixing

For binary systems

When a mixture is formed, energy change occurs because interactions between like and unlike

molecules are different.

Heats of mixing are generally much smaller than heats of reaction.

Enthalpy / Concentration Diagrams H2SO4 / H2O

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Enthalpy is plotted as a function of composition

at a given temperature ( P = 1 atm )

Reference state:

H1 = 0 for pure liquid H2SO4 at 25C

H2 = 0 for pure liquid H2O at 25C

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Heats of solution

H is the heat effect per 1 mole of solution

H / x1 is the heat effect per 1 mole of solute
heat of solution per mole of solute

For example, when 1 mole of LiCl is dissolved in 12 mole of H2O at 25C

LiCl(s) + 12H2O(l)  LiCl(12H2O) = –33,614 J

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Example 11.3 The heat of formation of LiCl in aqueous solution at 25C

Li + ½Cl2  LiCl(s) = –408,610 J

LiCl(s) + 12H2O(l)  LiCl(12H2O) = –33,614 J

Li + ½Cl2 + 12H2O(l)  LiCl(12H2O) = –442,224 J

NOT including the heat of the formation of water

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