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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008 Lecture #14 page 1

Multicomponent Systems, Partial Molar Quantities,

and the 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 or a biochemical process?

• 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 ≡ ⎜ ⎟ as 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 2008 Lecture #14 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,
(for example a solid and a liquid phase, or for the case of a cell
placed in salt water, the water in the cell versus the water out of
the cell in the salt water)

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 )

dG = ⎡⎣ µ1(b ) − µ1(a ) ⎤⎦ dn1

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
5.60 Spring 2008 Lecture #14 page 3

For the cell in a salt water solution, µ water (cell ) (T , p ) > µ water (solution ) (T , p ) and
the cell dies as the water flows from the cell to the solution (this is
what we call osmotic pressure)

The chemical potential and its downhill drive to equilibrium will be

the guiding principle for our study of phase transitions, chemical
reactions, and biochemical processes

• Partial molar quantities

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

⇒ n1 µ1 + n2 µ2 = G
5.60 Spring 2008 Lecture #14 page 4

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

⎛ ∂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

Consider 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 )
5.60 Spring 2008 Lecture #14 page 5

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

Dalton’s Law

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 X A
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. This
is at heart a reflection about entropy, the chemical potential of “A”
in the mixture is less than if it were pure, under the same (T,p)
conditions, because of the underlying (but hidden in this case)
entropy change!