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Lecture #17

Lecture 17
Objectives:
1. Notation of chemical reactions
2. General equilibrium
3. Be able to derive the chemical equilibrium constants from statistical mechanics.
4. Identify how nonideal behavior can be accounted for in chemical reactions.
1. Notation of chemical reactions:
Consider the chemical reaction
Cl2 + H2
2HCl
The numbers in front of the chemical formulae are the stoichiometric coefficients, which are
always positive. We can use the coefficients to define the stoichiometric numbers, i . By
convention we take the sign to be positive for products (terms on the right), negative for
reactants (terms on the left), and zero for inert species. Hence, Cl2 = H2 = 1 and
HCl = 2. Thus, we can write a single chemical reaction as
C
X

i Mi = 0

i=1

where Mi is the chemical formula for component i. What are the stoichiometric numbers for
3A + 2B
4C?
We can write a relationship for the number of moles of a component present at a given time,
and the initial number of moles of that component present before the reaction takes place.
The relationship is cast in terms of the extent of reaction, .
ni = ni0 + i
2. General Equilibrium Formulation:
At constant pressure and temperature the criterion for general equilibrium is a minimum in
the Gibbs free energy:
min G =

nk ,xki

C X
X

i=1 k=1

nki ki =

C X
X

nk xki ki

i=1 k=1

where nk is the number of moles in phase k, xki is the mole fraction of component i in phase k,
and ki is the chemical potential of component i in phase k. Note that the only variables we
have available to manipulate are the total number of moles and mole fractions for each phase.
There are also some constraints on the above equation which must be taken into account.
The constraints are:

Lecture #17
(a) Material balance

ni =

nki =

nki0 +

il l

(i = 1, . . . , C)

k=1 l=1

k=1

k=1

R
X
X

(b) Non-negativity
nk 0
1

(k = 1, . . . , )

xki

(i = 1, . . . , C; k = 1, . . . , )

If we hold the temperature and the volume constant instead then the equilibrium condition
is a minimum in the Helmholtz free energy:
min A = min {P V +
nk ,xki

nk ,xki

ki nki }

Consider a single phase, single chemical reaction. The Gibbs free energy is given by
G=

C
X

n i i =

C
X

ni0 i +

i i

i=1

i=1

i=1

C
X

Then note that

dni = i d
We want to find


G
ni

=0

(i = 1, C)

T,P

but,
dG = SdT + V dP +

C
X

i dni = SdT + V dP +

i=1

At constant T, P we have
dG =

C
X

i i d

i=1

So to find the minimum we need to find



=0
T,P

Hence, the condition for chemical equilibrium is

C
X

i i = 0.

i=1

This is true for any chemical reaction at equilibrium.

C
X
i=1

i i d

Lecture #17
3. Reactions in ideal gases
The standard free energy equilibrium constant in classical thermodynamics is
X

RT ln Keq =

rxn
i i = G

where superscript refers to the chemicals in their standard states. What is meant by standard
states? it is generally taken to refer to unit pressure (i.e., 1 bar) or unit fugacity at the
is the change in free energy of reaction per mole of the
temperature of the reaction. G
rxn
molecules in their standard states,
=
G
rxn

=
i G
i

i i ,

i = i .
where we have used the fact that for a pure fluid G
Recall that in classical thermodynamics we define Keq in terms of fugacities,
Keq =

fi
fi

Y
i

! i

where f is the standard state fugacity. For an ideal gas the equilibrium constant gives a
direct measure of the equilibrium conversion through the mole fractions.
Keq =

Y  yi p  i

The goal is to compute Keq from statistical mechanics. To do this we need an expression for
i from statistical mechanics. Recall that
= kT

ln Q
N

V,T

Invoking the semi-classical partition function,

Q=

N
Zqint
3N N !

where
qint = qe qv qr
Assume that at the standard state the molecules are ideal gases. This is usually a good
approximation at high temperatures and pressures of 1 bar. Then Z = V N and we can write
i

V qint,i
= kT ln
N 3i

where V is the volume in the standard state. Recognizing that V /N = kT /P we have

i = NA i = RT ln kT qint,i
G
P 3i

Lecture #17

where NA is Avogadros number and we have recognized that the molar Gibbs free energy is
just NA times the molecular (not molar) chemical potential of the pure fluid.
Thus,
Keq =

qint,i kT
P 3i

Y
i

where =

i i

! i

kT
P

 Y
i

qint,i
3i

! i

and P = 1 bar.

4. Example: Association in sodium vapor.

Consider the gas phase association reaction
2Na
Na2
The equilibrium constant can be written as
K(T ) =

P (qint,Na2 /3Na2 )
PNa2 P
=
2
kT (qint,Na /3Na )2
PNa

The electronic ground state of Na is doubly degenerate ( = 2).

qint,Na2
=
3Na2
qint,Na
=
3Na

2mNa2 kT
h2

2mNa kT
h2

3/2 

3/2

T
2r

exp(D0 /kT )
1 exp(v /T )

qelec

Plugging in the numbers and using T = 1000 K we get

K(T = 1000) = 0.493
The experimental value is 0.469.
5. Nonideal mixture behavior in fluid phase reactions.
(a) Recall that at equilibrium
C
X

i i = 0.

i=1

This expression is valid for ideal and nonideal solutions. For any real (or ideal) fluid we
can write the chemical potential as
i =

fi
+ RT ln
fi

= i + RT ln ai ,

where i is a function of temperature only and ai = xi i and i is the activity coefficient.

Let i on a per mole basis be given by
kT qint,i
i = RT ln
P 3i

Lecture #17
Then the equilibrium equation becomes
C
X

i (i + RT ln ai ) =

C
X

C
X

C
X

kT qint,i
i ln
i i = RT
P 3i
i=1
i=1
ln

i=1

ln

"

kT qint,i
P 3i

C
Y

! i

kT qint,i
P 3i

i=1

K(T ) =

C
Y

C
X

i RT ln ai = 0

i=1

i=1

i=1

C
X

C
X

i i +

+ RT

C
X

i ln ai = 0

i=1

ln (ai )i

i=1

! i #

= ln

C
Y

ai i

i=1

ai i

i=1

Now you can calculate K(T ) from statistical mechanics as before, but use some liquid phase activity coefficient model for ai to correct for nonideal behavior to find the
composition.
6. Gas phase nonidealities.
For reactions in nonideal gases we use the fugacity to relate the equilibrium constant to the
compositions:
K=

fi
fi

Y
i

! i

If we assume unit fugacity as the reference state this becomes

K=

Y   i

fi

= Kf

Introducing the fugacity coefficients we have

K=

Y

i yi P

 i

= KKy P

where
K =

i i

7. Condensed phases:
Substitute ai = i xi to get
Keq =

Y
i

(i xi )i =

Y
i

ii

Y
i

xi i = K Kx

Lecture #17

If you know Keq and have an expression for i you can use this equation to solve for the
equilibrium composition in a nonideal liquid phase reaction. The problem is nonlinear in the
mole fractions and must be solved numerically.
If on the other hand you know the equilibrium constant and can measure several equilibrium
compositions you can fit the parameters for an activity coefficient model. Walas shows how
to do this.