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.