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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #16

page 1

Equilibrium in Solution
The chemical potential for molecules in solution is given by a formula that is very similar to that for ideal gases:
o o A (T , p , cA ) = A (T , p ) + RT ln cA = A (T , p ) + RT ln [A ]

o The precise definition of the standard chemical potential A (T , p ) is

now more complicated; it is defined at a given pH, salt concentration, etc, all solution properties that need to be defined in advance. We will not go through those and take it as a given that the standard state is appropriately defined.
o Given a standard chemical potential A (T , p ) , then the analysis that

we did for the ideal gas follows straight through and we find for a solution process

A A(sol, T, p) + B B(sol, T, p) = C C(sol, T, p) + D D(sol, T, p)

that following the ideal gas analysis in our previous lecture
[C ]C [D ]D o o o o G ( ) = C C (T ) + D D (T ) A A (T ) + B B (T ) + RT ln [A ] A [B ] B

and the equilibrium constant K comes out through

o Grxn = RT ln K ,

K = e G
C D
B

RT

Where K = Qeq

[C ] [D ] at equilibrium as before, and where the = [A ] [B ]

A

concentrations are equilibrium concentrations.

5.60 Spring 2008

Lecture #16

page 2

Temperature dependence of K (or Kp)

ln K (T ) = G o

RT

d ln K d G o G o 1 d G o = = dT dT RT RT 2 RT dT

But at fixed pressure and/or solutions properties (p = 1 bar, pH constant, etc..)

d G o G o = dT T 1 bar,pH constant, etc...

and from fundamental equation

G dG = SdT +Vdp = S T p

G o o = S (T T p

o o 1 d ln K H (T ) T S (T ) = + S o (T 2 dT RT RT

d ln K (T ) H o (T = dT RT 2

)
H o (T

Integrating: At constant p:

ln K (T2 ) = ln K (T1 ) +

T2

T1

RT

)dT

H o (T ) = H o (T1 ) + C p (T T1 )
T2

ln K ( 2 ) = ln K ( 1 ) + T T

H o ( 1 ) + C p ( T1 ) T T

T1

RT 2

dT

Over small T ranges, C p (T T1 ) can be assumed small and H o independent of T.

ln K (T2 ) ln K (T1 ) + H o 1 1 H o T2 T1 = ln K (T1 ) + R T1 T2 R TT2 1

5.60 Spring 2008

Lecture #16

page 3

If

H o (T ) < 0

(Exothermic)

T2 >T1 means K p (T2 ) < K p (T1 )

The equilibrium shifts toward reactants If

H o (T ) > 0 (Endothermic)

T2 >T1 means K p (T2 ) > K p (T1 )

The equilibrium shifts toward products This is Le Chateliers principle for Temperature

Example: The Haber process N2(g, T, p) + 3/2 H2(g, T, p) = NH3(g, T, p)

o Hrxn (298 K ) = 46.21 kJ/mol o Grxn (298 K ) = 16.74 kJ/mol

Kp =

3 1 pH 2 pN 2
2 2

pNH

=p

3 1 XH 2 XN 2
2 2

XNH

=e

(8.314 J/K-mol)(298 K )

16,740 J/mol

= 860

For p = 1 bar this is pretty good, lots of product. However, the reaction at room T is slow (this is kinetics, not thermodynamics). Raising T to 800 K can speed it up. But since H o (T ) < 0 (exothermic), Le Chatelier tells us that the equilibrium will shift toward the reactants. Indeed: What to do?
K p ( 800 K ) = 0.007

Note above

KX = p K p

5.60 Spring 2008

Lecture #16

page 4

Again use Le Chatelier, but with pressure! If we increase p, Eq. shifts toward products. Run reaction at high T and high p

For p = 1 bar, T = 800 K, Kp = 0.007

KX = XNH
2 3

3 1 X H 2 XN 2
2

= (1 ) K p = 0.007

But at p = 100 bar,

K X = (100 ) K p = 0.7

much better!

Heterogeneous Equilibria

If a product or reactant is a solid or liquid, it will not appear in the ratio of partial ps for Kp or in the concentrations if the equilibrium is in solution. However, it must be used in G. Why? Take

A A(s) + B B(g) = C C() + D D(g)

The solid and liquid are not mixed they are pure states.
G = C C ( s, pure, p ) + D D ( g, mix, p ) A A ( l , pure, p ) + B B ( g, mix, p )

And for () or (s)

C ( pure, p ) o ( pure )

(no p-dependence)

o o o o G = C C + D D A A B B + RT ln

pD D = G o + RT lnQ B pB

5.60 Spring 2008

pDD B pB Eq .

Lecture #16

page 5

Kp =

No A or C involved.

But we still have and

o o o o o Grxn = C C + D D A A B B

ln K p =

o Grxn

RT

e.g. the decomposition of limestone CaCO3 (s) = CaO (s) + CO2 (g) T = 25C

Calculate equilibrium vapor pressure at room T and elevated T. Data at 25C: Substance CaCO3 (s) CaO (s) CO2 (g) o (kJ/mol) -1128.8 -604.0 -394.36 Hfo (kJ/mol) -1206.9 -635.09 -393.51 At equilibrium,

G = ( CaO, s ) + ( CO2 , g) ( CaCO3 , s ) = o ( CaO, s ) + o ( CO2 , g) + RT ln pCO2 o ( CaCO3 , s ) = G o + RT ln K p where K p = pCO2 (at eq.)

The equilibrium constant includes only the gas, but G o includes the solids too.
G o (kJ/mol) = -604.0 394.4 (-1128.8) = 130.4 kJ/mol H o (kJ/mol) = -635.1 393.5 (-1206.9) = 178.3 kJ/mol

5.60 Spring 2008

Lecture #16

page 6

Equilibrium pressure:
ln K p = G o = 130, 400 J/mol = 52.50 (8.314 J/K-mol) (298.15 K )

RT

K p = 1.43x 10 23 bar

Nothing there at room T !

ln pCO2 (1100 K ) ln pCO2 (298 K ) +

Try 1100 K:

pCO

H o 1 1 R 1100 K 298 K 178, 300 J/mol 1 1 = 52.50 = 0.17 8.314 J/K-mol 1100 K 298 K (1100 K ) 0.84 bar

Theres probably some change in Hfo over such a wide T range, but clearly the equilibrium shifts dramatically.