Chemical Equilibrium

The PURPOSE of this course!!

Basic Review of Equilibrium Constants

Le Châtelier’s Principle
Solubility Products
Complex Formation
Protic Acids and Bases
Acid-Base Equilibrium
Equilibrium Constants
aA(phase) + bB(phase)  cC(phase) + dD(phase)

The concentrations of each reagent are constant at equilibrium,

even though individual molecules are constantly reacting.

Another way of saying this is that the reaction rate in one direction is
equal to the reaction rate in the reverse direction.

Recall Le Châtelier’s Principle and how changing reaction

components and conditions can alter equilibrium!
 The Equilibrium Expression
Consider a generic reaction
aA (phase) + bB(phase)  cC(phase) + dD(phase)

[C]c  [D]d
K = K is the equilibrium constant (unitless)
[A]  [B]
a b

Dissolved species are in molar (M) concentrations

Gaseous species partial pressures are in atmospheres
Pure liquids and pure solids have concentrations of 1.
Excess solvents, which do NOT participate in the reaction, also have
concentrations of 1.
Equilibrium constants are reaction, phase, temperature and pressure
dependent
 Manipulating Equilibrium Expressions
 If you write a reaction in reverse, the new K is the
inverse of the original K
aA (phase) + bB(phase)  cC(phase) + dD(phase)
[C]c  [D]d
K"Forward" = K is the equilibrium constant (unitless)
[A]  [B]
a b

1
cC(phase)  dD(phase)  aA(phase)  bB(phase) K"Rev erse" 
K"Forward"
 If we add reactions, K values are multiplied
K1
Rxn 1 : aA (phase) + bB(phase)  cC (phase) + dD(phase)
K2
Rxn 2 : eE (phase) + fF(phase)  gG (phase) + hH(phase)
If we add the reactions together, the new K (call it K new ) is..
K new = K1  K 2
Special Equilibrium Expressions

 Kw (dissociation of water)
 Ksp (solubility of salts in saturated solutions)
 Ka (acid dissociation)
 Kb (base hydrolysis)
 x (complex ion formation)
 Kredox (redox reaction) and Kd (distribution
coefficient). We’ll not spend much time with
these two in CHEM 361.
Solubility
Products
(Ksp)
 Solubility Products & Common Ion Effect

 Ksp applies to salts in dynamic equilibrium in saturated

solutions.

MnIx (SOLID)  nM+charge (aq ) + xI(aq

-charge
)
+charge n -charge x
Ksp = [M ]  [I ]
 The solution MUST be SATURATED!
 The [solid] cancels out as it is 1.
 You can calculate concentrations of the salt, or the
 component ions.
 This applies to dilute solutions in pure water, and
ignores pH or activity (topics for later)
 What is the concentration of the salt, and
each ion, in a saturated solution of silver
chloride?
 Consider using an I-C-E “table”!
 Write the reaction
 Write the Ksp expression
 Look up Ksp in standardized table
 Substitute in for ion concentrations?
 Solve algebraically!
 Concentrations are in molar (M) units, you may
need to convert to ppm, ppb, etc.
 “I-C-E” Table
AgCl(s)  +
Ag(aq) + -
Cl(aq)
Initial Conc.
(Molarity) 1 0 0
Change
(Molarity) 1 +x +x

 Equilibrium
Conc. 1 0+x 0+x
(Molarity)

Ksp = [Ag+ ]  [Cl- ]

At equilibrium (we ALWAYS solve at Equilibrium)
Ksp = [x]  [x]
 What is the ppb concentration sulfur in a
saturated solution of of copper (I)
thiocyanate?

 What is the maximum concentration of

calcium that can be present in a solution with
1.00 M phosphate ion?
Common Ion Effect…

 What if your now saturated solution contained

some ion before you added the salt?
 The pre-existing “common ion” influences the
solubility of the salt!
 Use the previous steps, with an I-C-E table!
 What is the solubility of silver chloride in 1uM
sodium chloride? Setup “I-C-E” table.
 “I-C-E” Table
AgCl(s)  +
Ag(aq) + -
Cl(aq)
Initial Conc.
(Molarity) 1 0 1.0E-6
Change
(Molarity) 1 +x +x


Equilibrium
Conc. 1 0+x 1.0E-6 + x
(Molarity)

K sp = [Ag+ ]  [Cl- ]
At equilibrium (we ALWAYS solve at Equilibrium)
K sp = [x]  [1.0E - 6 + x]
You will now have a quadratic to solve.
Let' s solve it!
What is the solubility of sodium phosphate
(also called trisodium phoshpate or TSP)
in a 1.0 mM solution of phosphate ion?
Complex Formation
 In many cases, particularly cases where
we have a salt with a multiply charged
anion (e.g. Zn, Cd, Pb, Fe, etc.),
complexes can form. These take the
form of.
(mn + xy)
n y
MmX x
 Where the complex itself can have a
zero or integer charge.
All of the reactants and products of these reactions
are in aqueous solution.

Complexes effectively remove free ions from solution

& increase the solubility of solids.
Acids and Bases (review)…
 Brønsted-Lowry Definition:
 Acids are proton donors
 Bases are proton acceptors
 Lewis Definition
 Acids are electron-pair acceptors
 Bases are electron-pair donors
 Arrhenius Definition
 Acids react in water to release a proton
 Bases react in water to release hydroxide ion
 Acid + Base  Salt + Water

 Acid + Base  Conjugate Base + Conjugate Acid

 Some solvents are amphiprotic

 Water can act as an acid and a base!
 Methanol can act as an acid and a base!

 Autoprotolysis
 Some solvents can react with themselves to produce an acid and a
base
 Water is a classical example

 Weak acids dissociate partially, weak bases undergo partial

hydrolysis. Strong acids and bases are strong electrolytes.
Kw (Dissociation of Water)
 Water is amphiprotic it also undergoes autoprotolysis
Kw
H2O + H2O  H3O +
+ OH-
Base Acid Conjugate Acid Conjugate Base

K w  [H3O] x [OH- ]
 Kw = 1.0E-14 at about 25 ˚C
 This is where the pH scale we commonly use originates
from!

 What is the concentration of hydronium and hydroxide

ions in neutral solution? What is the pH? What is the
pOH?
Weak Acid & Weak Base Equilibria

 Weak acids produce weak conjugate

bases, and weak bases produce weak
conjugate acids
 Ka is a “special” equilibrium constant for
the dissociation of a weak acid (found in
standard tables)
 Kb is a “special” equilibrium constant for
the hydrolysis (or dissociation” of a weak
base.
 HA (aq) + H2O(l)  H3O+(aq) + A(aq)
-

[H3O+(aq) ] x [A(aq)
-
]
Ka =
[HA (aq) ]

NH3(aq) + H2O(l)  NH4+(aq) + OH(aq)

-

[NH4+(aq) ] x [OH(aq)
-
]
Kb =
[NH3(aq) ]

FOR ANY Conjugate Acid - Base Pair in Aqueous Solution

Ka x Kb = Kw
Only Ka values appear in most standardized tables.
Calculations……..
 What is the pH of a 1.0 M solution of acetic acid
(HAc)?

 What assumption can you make?

 If [acid] is about 1000 times the Ka value, it’s concentration
in solution won’t change much!
 Use an “I-C-E” table to look at this.
 The text goes into a more elaborate discussion of
approximations. I will allow approximations if the
concentrations or pH values do not change in the hundred’s
decimal place.
 What is the pH of a 4.0 M solution
of phosphate ion?
 Writereaction
 Calculate Kb
 Setup “I-C-E” table
 Make assumptions
 Solve algebraically.
Buffers
 Buffers resist the change in pH because
they have acid to neutralize bases and
bases to neutralize acids.
 Made from a weak acid (HA) and the salt
of its conjugate base (A-, where the
counter ion is gone for example), or a
weak base and the salt of its conjugate
acid.
Features of Buffers
 Buffers work best at maintaining pH
near the Ka of the acid component,
usually about +/- 1 pH unit. This is their
buffer capacity .
 Buffers resist pH changes due to
dilution.
 All seen when we use the “Buffer
Equation”
Henderson-Hasselbalch (Buffer) Equation
 A modification of the equation for the dissociation of a
 A 
 
weak acid. -
pH = pKa + log  
HA  
 
 The pH is the pH of the buffered solution, pKa is the pKa
of the weak acid.
 What is the pH of a buffer solution made from 1.0 M acetic
acid and 0.9 M sodium acetate?


You add .10 moles of sodium hydroxide to the above
solution? What is the new pH?
H-H Equation & Buffers….

 If [A-] = [HA] pH = pKa!

 This is what we see at half-way to the
equivalence point in the titration of a weak
acid with a strong base!
 Dilution does not change the ratio of A-
to HA, and thus the pH does not change
significantly in most cases
 How do you prepare buffers?
 Select a buffer ‘system’ based on the pH you want to
maintain.
 Use the H-H equation to calculate how much acid and
conjugate base you need
 Take one of three approaches:
 Mix acid and base forms, measure pH and adjust with strong acid or
strong base
 Start with a solution of weak acid, and add strong base until you reach
the desired pH
 Start with a solution weak base and add strong acid until you reach the
desired pH
 REMEMBER, STRONG Acids or Bases react completely!
 Dilute as necessary, adjust pH further if needed with strong
acid or base.
 You want 1L of a buffer system that has
a pH of 3.90?
 What acid/conjugate base pair would you
use?
 How would you go about figuring out how
much of each reagent you might need?
 How would you prepare and adjust the pH
of this solution?
What about “canned” buffer systems (e.g. Tris)?
 Commercially available acid/base forms
 Pre-determined mixing ratios.
 Very convenient, used in biological studies,
cultures, cell growth media, etc.
 Tris = Tris (hydroxymethyl) aminomethane

TRIS base form.