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Partial Molar Properties

1. The fundamental equations relating changes in internal energy, enthalpy, Gibbs free energy, and Helmholtz free energy are modified for open systems where mass and composition can change. The new equations include terms for the chemical potential of each component multiplied by its change in amount. 2. The chemical potential of a component is defined as the partial molar Gibbs free energy. At equilibrium between phases, the chemical potential of each component must be equal in all phases. 3. Extensive properties like the Gibbs free energy of a system can be expressed as the sum of each component's partial molar quantity multiplied by its amount. Partial molar quantities are also defined for enthalpy, internal energy, and

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142 views5 pages

Partial Molar Properties

1. The fundamental equations relating changes in internal energy, enthalpy, Gibbs free energy, and Helmholtz free energy are modified for open systems where mass and composition can change. The new equations include terms for the chemical potential of each component multiplied by its change in amount. 2. The chemical potential of a component is defined as the partial molar Gibbs free energy. At equilibrium between phases, the chemical potential of each component must be equal in all phases. 3. Extensive properties like the Gibbs free energy of a system can be expressed as the sum of each component's partial molar quantity multiplied by its amount. Partial molar quantities are also defined for enthalpy, internal energy, and

Uploaded by

Rojo John
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We take content rights seriously. If you suspect this is your content, claim it here.
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5.

60 Spring 2005 Lecture #16 page 1

Multicomponent Systems, Partial Molar Quantities,


and Chemical Potential
So far we’ve worked with fundamental equations for a closed (no
mass change) system with no composition change.

dU =TdS − pdV dA = −SdT − pdV


dH =TdS +Vdp dG = −SdT +Vdp

How does this change if we allow the composition of the system to


change? Like in a chemical reaction

• Consider Gibbs free energy of a 2-component system G (T , p ,n1 ,n2 )

⎛ ∂G ⎞ ⎛ ∂G ⎞ ⎛ ∂G ⎞ ⎛ ∂G ⎞
⇒ dG = ⎜ ⎟ dT + ⎜ ⎟ dp + ⎜ ⎟ dn1 + ⎜ ⎟ dn2
⎝ ∂T ⎠ p ,n ,n ⎝ ∂p ⎠T ,n ,n ⎝ ∂n1 ⎠T , p ,n ⎝ ∂n2 ⎠T , p ,n

1 2
 1
2 
2 
1
−S V µ1 µ2

⎛ ∂G ⎞
We define µi ≡ ⎜ ⎟ the chemical potential of species “i”
⎝ ∂ni ⎠T , p ,nj ≠i

µi (T , p , nj ) is an intensive variable

This gives a new set of fundamental equations for open systems


(mass can flow in and out, composition can change)

dG = −SdT +Vdp + ∑ µi dni


i

dH =TdS +Vdp + ∑ µi dni


i

dU =TdS − pdV + ∑ µi dni


i

dA = −SdT − pdV + ∑ µi dni


i
5.60 Spring 2005 Lecture #16 page 2

⎛ ∂G ⎞ ⎛ ∂H ⎞ ⎛ ∂U ⎞ ⎛ ∂A ⎞
µi = ⎜ ⎟ =⎜ ⎟ =⎜ ⎟ =⎜ ⎟
⎝ ∂ni ⎠T , p ,nj ≠i ⎝ ∂ni ⎠S , p ,nj ≠i ⎝ ∂ni ⎠S ,V ,nj ≠i ⎝ ∂ni ⎠T ,V ,nj ≠i

• At equilibrium, the chemical potential of a species is the same


everywhere in the system

Let’s show this in a system that has one component and two parts,
e.g. a solid and a liquid phase.

Consider moving an infinitesimal amount dn1 of component #1 from


phase a to phase b at constant T,p. Let’s write the change in state.

dn1 (T , p ,phase a ) = −dn1 (T , p ,phase b )

0 0
dG = −S dT +V dp + ∑ µi dni = ⎡⎣ µ1(b ) − µ1(a ) ⎤⎦ dn1
i

µ1(b ) < µ1(a ) ⇒ dG < 0 ⇒ spontaneous conversion from (a) to (b)


µ1( a ) < µ1(b ) ⇒ dG > 0 ⇒ spontaneous conversion from (b) to (a)

At equilibrium there cannot be any spontaneous processes, so

µ1(a ) = µ1(b ) at equilibrium

e.g. liquid water and ice in equilibrium

µ ice (T , p ) = µ water (T , p )
ice
at coexistence equilibrium
water

This will be the guiding principle for our study of phase transitions
and chemical reactions.
5.60 Spring 2005 Lecture #16 page 3

• Partial molar quantities

µi is the Gibbs free energy per mole of component “i”, or the


partial molar Gibbs free energy

⎛ ∂G ⎞
⎜ ⎟ = µi = Gi
⎝ ∂ni ⎠T , p ,nj ≠i

G = n1 µ1 + n2 µ2 + " + ni µi = ∑ ni µi = ∑ ni Gi
i i

Let’s prove this, using the fact that G is extensive.

G (T , p , λn1 , λn2 ) = λG (T , p , n1 , n2 )
dG
(T , p , λn1 , λn2 ) = G (T , p , n1 ,n2 )
dλ

⎛ ∂G ⎞ ⎛ ∂ ( λn1 ) ⎞ ⎛ ∂G ⎞ ⎛ ∂ ( λn2 ) ⎞
⎜⎜ ⎟⎟ ⎜ ⎟ +⎜ ⎟⎟ ⎜ ⎟ =G
⎜
⎝ ∂ ( λn1 ) ⎠T , p ,λn2 ⎝ ∂λ ⎠T , p ,λn2 ⎝ ∂ ( λn2 ) ⎠T , p ,λn1 ⎝ ∂λ ⎠T , p ,λn1



n1 n2

λ is arbitrary, we can choose λ = 1

⇒ n1 µ1 + n2 µ2 = G

We can define other partial molar quantities similarly.

⎛ ∂A ⎞
⎜ ⎟ = Ai ⇒ A = n1A1 + n2A2 + " + ni Ai = ∑ ni Ai
⎝ ∂ni ⎠T , p ,nj ≠i i

partial molar Helmholtz free energy

⎛ ∂A ⎞
note what is kept constant ⇒ not to be confused with ⎜ ⎟ = µi
⎝ ∂ni ⎠T ,V ,n j ≠i
5.60 Spring 2005 Lecture #16 page 4

⎛ ∂H ⎞
⎜ ⎟ = Hi ⇒ H = n1H1 + n2H2 + " + ni Hi = ∑ ni Hi
⎝ ∂ni ⎠T , p ,n j ≠i i

partial molar enthalpy

⎛ ∂U ⎞
⎜ ⎟ = Ui ⇒ U = n1U1 + n2U2 + " + niUi = ∑ niUi
⎝ ∂ni ⎠T , p ,n j ≠i i

partial molar energy


__________________________________________________

Let’s compare µ of a pure ideal gas to µ in a mixture of ideal gases.

• Chemical potential in a pure (1-component) ideal gas

p p
From G (T , p ) = G o (T ) + RT ln ⇒ µ (T , p ) = µ o (T ) + RT ln
p0 p0

• Chemical potential in a mixture of ideal gases

onsider the equilibrium Fixed Partition


mixed pure
pA′ + pB′ = ptot A,B A
p'A, p'B pA
\
At equilibrium µA ( mix ,T , ptot ) = µA ( pure ,T , pA )

Also pA ( pure ) = pA′ ( mix ) = ptot XA

Dalton’s Law
5.60 Spring 2005 Lecture #16 page 5

So
µA (mix ,T , ptot ) = µA ( pure ,T , ptot XA )
⎛p X ⎞
= µAo (T ) + RT ln ⎜ tot A ⎟
⎝ p0 ⎠
ptot
= µAo (T ) + RT ln + RT ln XA
p0

µA ( pure ,T , ptot )

∴ µA ( mix ,T , ptot ) = µA ( pure ,T , ptot ) + RT ln XA

Note XA < 1 ⇒ µA (mix ,T , ptot ) < µA ( pure ,T , ptot )

The chemical potential of A in the mixture is always less than the


chemical potential of A when pure, at the same total pressure.

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