Chemistry 2402 - Thermodynamics

Lecture 13 : Non Ideal Solutions and Activity

Lecture 14 : Chemical Equilibria

Lecture 15 : Kinetic Coefficients & the Transition State

 Equilibrium when Conversion of Chemical Species is
Allowed – i.e. Chemistry

Consider the generic chemical equilibrium

aA + bB  cC + dD

The Gibbs free energy is given by

G = NAA + NBB + NC C + NDD

and a change in the Gibbs free energy is

dG = dNAA + dNBB + dNC C + dNDD

 Chemical Equilibria (cont.)
Here is where the only bit of information about the chemical reaction enters.
The stoichiometry requires the following relationship between the various
changes in species number -

dN C dN D dN A dN B
    d
c d a b

The term d is introduced just to help with notation. With this relation we
can now simplify the expression for dG,

dG = (cC+ dD - aA - bB)d

At equilibrium dG = 0 and we have the condition

cC + dD = aA + bB

 Chemical Equilibrium in the Ideal Gas Mixture
We can now substitute in our expression for the chemical potential for the
ideal gas mixture,
i = io + kBTln(Pi/atm)

which, on rearranging, gives

G o   RT ln K P

where G o  N ( c Co  d Do  a Ao  b Bo ) , N is Avogadro's number and

( PC / atm) c ( PD / atm) d
KP 
( PA / atm) a ( PB / atm) b

Note that KP is independent of pressure and dependent on the ideal gas

assumption.
 Temperature Dependence of KP

 ln K P    G o  H o
    van't Hoff's equation (differential form)
T T  RT  RT 2
P

If we can assume that Ho is independent of temperature then we can

integrate this equation to give

 K P (T2 )  H o 1 1
ln        van't Hoff's equation (integrated form)
 P 1 
K (T ) R  T2 T1 

This result indicates that for exothermic reactions increasing the

temperature, decreases KP and vice versa for endothermic reactions.
Flash Quiz!

Using the example of an exothermic reaction,

explain how van’t Hoff’s equation is consistent
with the predictions of Le Châtelier’s principle.

 ln K P H o

T
P 2
RT
 Using the example of an
Answer exothermic reaction, explain
how van’t Hoff’s equation is
consistent with the predictions
of Le Châtelier’s principle.

 ln K P H o If a change is applied to a
 chemical system at equilibrium;
T
P 2 the equilibrium will shift in order
RT to partially counteract the
imposed change.

• Exothermic → Ho < 0 • ↑T → reaction to shift to cool

the system (i.e. in the
• Therefore Kp goes down endothermic direction)
with increased • For an exothermic reaction,
temperature this shifts toward the reactants,
so Kp goes down
 Chemical Equilibria In Solution

Starting with the same reaction aA + bB  cC + dD we arrive at the same

equilibrium condition

cC + dD = aA + bB

Substituting in the expression for the chemical potential of the non-ideal

solution

i(sol) = iө(sol) + kBTln(ai(sol))

where the reference state is a 1 molar solution of the species i in the solvent.
 Chemical Equilibria in Solutions (cont.)

This results in the following relation

ΔGө = - RTlnKa

where Gө = N(cμCө + dμDө - aμAө -bμBө)

and
aCc a Dd
Ka  a b
a Aa B
or
xCc xDd  Cc  Dd
Ka  a b a b
x A xB  A B
Note that the expression for the equilibrium constant in terms of
concentrations is only valid for the ideal solution.
 Example: Solubility of Sparingly Soluble Salts

Consider the case of a sparingly soluble salt like silver chloride

AgCl(s) ↔ Ag+(aq) + Cl-(aq)

At equilibrium (i.e. a saturated solution)

μAgCl(s) = μAg+ө +kBTln a(Ag+) + μCl-ө + kBTln a(Cl-)

Or
a(Ag+) a(Cl-) = Ks the solubility product
 Sparingly Soluble Salts (cont.)

Writing the solubility product in terms of activity coefficients gives

Ks = [γ(Ag+) γ(Cl-)] x(Ag+) x(Cl-)

Since the concentration of dissolved salt is low we typically find the

activity coefficients are close to 1.

If, however, we add extra salt with no ion in common e.g. KNO3 then
we find that the activity coefficients are less than 1.

Since Ks is a constant, this means the concentration of ions must

increase – i.e. the solubility increases due to the added salt.
 Sample exam questions from
previous years
• At room temperature (25 °C), calcium carbonate has an aqueous
solubility product of Ksp = 4.47×10-9 M2.
– Calculate the calcium concentration in a saturated solution of calcium
carbonate in pure water at room temperature. State any assumptions or
approximations you make.
– Sea water has a high concentration of aqueous NaCl. This reduces the
activity ratio of calcium ions to 0.405, and carbonate ions to 0.370.
Calculate the calcium concentration in a saturated solution of calcium
carbonate in sea water at room temperature.
• Using the example of an exothermic reaction, explain how van’t Hoff’s
equation is consistent with the predictions of Le Châtelier’s principle.
• The equilibrium constant for the gas phase reaction H2 + I2  2HI is
45.6 at 764 K and 60.8 at 667 K. Assuming that the heat of reaction is
constant over this temperature range, calculate the enthalpy change
which accompanies one mole of the forward reaction.
Summary
You should now
• Understand the connection between the standard free energy
of a reaction, and its equilibrium constant
• Calculate one from the other
• Understand the conditions under which the integrated form of
Van’t Hoff’s equation is valid
• Apply Van’t Hoff’s equation to calculate the change in an
equilibrium constant as temperature is changed
• Explain how “spectator ions” can affect the solubility of a salt in
a non-ideal solution

Next Lecture
• Kinetic Coefficients & the Transition State