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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 weve worked with fundamental equations for a closed (no mass change) system with no composition change.
dU =TdS pdV dH =TdS +Vdp dA = SdT pdV 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 G G G dG = dT + dp + dn1 + dn2 p T ,n ,n n1 T , p ,n n2 T , p ,n T p ,n ,n  

1 2

G (T , p , n1 , n2 )

1 2  

2  

1  

We define

G ni T , p ,nj i

as the chemical potential of species i

i (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 + i dni dH =TdS +Vdp + i dni dU =TdS pdV + i dni dA = SdT pdV + i dni
i i i i

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i =

G H U A = = = 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 Lets 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. Lets write the change in state.

dn1 (T , p ,phase a ) = dn1 (T , p ,phase b )
(b ) (a ) dG = 1 1 dn1

1(b ) < 1(a ) dG < 0

spontaneous conversion from (a) to (b) spontaneous conversion from (b) to (a)

1(a ) < 1(b ) dG > 0

At equilibrium there cannot be any spontaneous processes, so

1(a ) = 1(b ) at equilibrium

e.g. liquid water and ice in equilibrium ice water

ice (T , p ) = water (T , p )

at coexistence equilibrium

5.60 Spring 2008

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For the cell in a salt water solution, water (cell ) (T , p ) > 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

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

partial molar Gibbs free energy

G = i = Gi
ni T
, p ,nj i

G = n1 1 + n2 2 + " + ni i = ni i = ni Gi

Lets prove this, using the fact that G is extensive.

G (T , p , n1 , n2 ) = G (T , p , n1 , n2 ) dG (T , p , n1 , n2 ) = G (T , p,n1 ,n2 ) d
G G ( n1 ) ( n2 ) + =G ( n ) T , p ,n ( n2 ) T , p ,n 1 T , p , n2 T p n , , 2 1 1   
  

n1 n2

n1 1 + n2 2 = G

5.60 Spring 2008

Lecture #14

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We can define other partial molar quantities similarly.

A = Ai ni T , p ,nj i

A = n1A1 + n2A2 + " + ni Ai = ni Ai

i

partial molar Helmholtz free energy note what is kept constant

H = Hi ni T , p ,n j i

not to be confused with ni T ,V ,n

i

= i
j i

H = n1H1 + n2H2 + " + ni Hi = ni Hi

partial molar enthalpy

U
= Ui ni T , p ,n j i

U = n1U1 + n2U2 + " + niUi = niUi

i

partial molar energy __________________________________________________ Lets compare of a pure ideal gas to in a mixture of ideal gases. Chemical potential in a pure (1-component) ideal gas From
G (T , p ) = G o (T ) + RT ln p p0

(T , p ) = o (T ) + RT ln

p p0

Chemical potential in a mixture of ideal gases Consider the equilibrium

+ pB = ptot pA

mixed pure A A,B p'A, p'B pA

\

Fixed Partition

At equilibrium

A ( mix ,T , ptot ) = A ( pure ,T , pA )

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Also

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

Daltons Law

So

A (mix ,T , ptot ) = A ( pure ,T , ptot XA )

p X o = A (T ) + RT ln tot A p0
o = A (T ) + RT ln

ptot + RT ln X A p0

A ( pure ,T , ptot )

Note

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

XA < 1

A (mix ,T , ptot ) < A ( 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!