Chemical Equilibria PDF

Chemical Equilibria
Dr. Kathlia A. De Castro-Cruz

Analytical Chemistry for CHE 1
Acids vs Base
Ø Acids
ü Have sour taste
ü React with certain metals to produce hydrogen
gas.
ü React with carbonates and bicarbonates to
produce carbon dioxide gas.
Ø Bases
ü Have bitter taste
ü Feel slippery
kadecastro-cruz 2 Chemical Equilibria

Acid-Base Definitions
Ø Arrhenius
ü Any substance which ionize in water to
produce hydronium ion (H3O+) is ACID
−
H 2 SO4 + H 2O → HSO4 + H 3O+
ü Any substance which ionize in water to

€ produce hydroxide ion (-OH) is BASE
+ −
NaOH + H 2O → Na aq + OH aq

€
Ø Lewis
ü Electron pair acceptor is ACID
ü Electron pair donor is BASE
H
O + H Cl O + Cl
H H
H H
Electron Pair Electron Pair
Donor Acceptor
Base Acid

Ø Brønsted-Lowry
ü Proton donor is ACID
ü Proton acceptor is BASE
ü Works for non aqueous solutions
NH3(g) + H2O(l) NH4+(aq) + OH-(aq)

Base: Acid:
H+ acceptor H+ donor

Ø Practice Problem:
ü Classify the following species as Bronsted
acid or base, or both based on their reaction
with water: HCN, Cl-, NH3, ClO4-, HSO4-
ü Classify each of the following as Lewis acid
or Lewis base: BF3, -OH, NH3, H2O

Brønsted-Lowry Concept
Ø Categories
ü Strong acids and bases almost completely
ionize
HNO3(aq) + H2O(l) H3O+(aq) + NO3-(aq)
ü Weak acids and bases do not fully ionize

HF(aq) + H2O(l) H3O+(aq) + F-(aq)
H2O(l) + NH3(aq) NH4+(aq) + OH-(aq)
Acid: Base: Acid: Base:
H+ donor H+ acceptor H+ donor H+ acceptor
v Note: the products are a new acid and base pair
Conjugate Acid-Base Pairs
Ø Molecules or ions related by the loss/gain of
one H+.
Conjugate Acid Conjugate Base
H3O+ H2O
CH3COOH CH3COO-
donate H+
NH4+ NH3
H2SO4 HSO4-
accept H+
HSO4- SO42-
HCl Cl-


Ø Practice Problem: Given the following
reactions identify the conjugate acid-base
pairs:
a. HONH 2 + H 2O ↔ HONH 3 + + −OH

b. HSO4 − + H 2O ↔ SO4 2− + H 3O+
2− − −
c. HC2 H 3O2 + CO3 ↔ HCO3 + C2 H 3O2
€
Classification of Acids & Bases
Ø According to strength
ü Strong acids/Strong bases
q Are strong electrolytes, which are assumed to
ionize completely in water
ü Weak acids/Weak bases
q Ionize only to limited extent in water, they are
weak electrolytes

Ø Strong vs Weak Electrolytes

Strong Electrolytes Weak Electrolytes
Inorganic acids such as Inorganic acids such as
HNO3, HClO4, H2SO4, HCl, H2CO3, H3BO3, H3PO4,
HBr, HCl3, HBrO3 H2S, H2SO3
Alkaline and alkaline earth

Most organic acids
hydroxides
Ammonia and most organic
Most salts
bases
Halides, cyanides,
thiocyanites of Hg, Zn and Cd
H2SO4 is strong only on the first ionization
Strong Electrolyte – 100% dissociation

H2O
NaCl (s) Na+ (aq) + Cl- (aq)
Weak Electrolyte – not completely dissociated
CH3COOH CH3COO- (aq) + H+ (aq)


ü Strong acids are strong electrolytes
HCl (aq) + H2O (l) H3O+ (aq) + Cl- (aq)
HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)
HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq)
H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)


ü Weak acids are weak electrolytes
HF (aq) + H2O (l) H3O+ (aq) + F- (aq)
HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq)
HSO4- (aq) + H2O (l) H3O+ (aq) + SO42- (aq)
H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)


ü Strong bases are strong electrolytes
H2O
NaOH (s) Na+ (aq) + OH- (aq)
H2O
KOH (s) K+ (aq) + OH- (aq)
H2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)


ü Weak bases are weak electrolytes
F- (aq) + H2O (l) OH- (aq) + HF (aq)
NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)
• H3O+ is the strongest acid that can exist in aqueous

solution.
• The OH- ion is the strongest base that can exist in aqueous
solution.
Ø According to number of replaceable H+ and

-OH
ü Monoprotic/monobasic
q Each unit of acid or base yields one hydrogen or
hydroxide upon ionization
→ H O + + CH COO -
CH 3COOH + H 2 O ← 3 3
→ NH +4 + OH -
NH 3 + H 2O ←

€

-OH
ü Diprotic/Dibasic
q Each unit of acid or base yields two hydrogen or
hydroxide upon ionization
+ −
H 2 SO4 → H + HSO4
− + 2−
HSO4 ↔ H + SO4
2+ −
Ba(OH) 2 → Ba + 2HO


-OH
ü Triprotic/Tribasic
q Each unit of acid or base yields three hydrogen
or hydroxide upon ionization
+ −
H 3 PO4 → H + H 2 PO4
− + 2−
H 2 PO4 ↔ H + HPO4
2− + 3−
HPO4 → H + PO4

Acid & Base Relative Strength
Ø Strong acids are better H+ donors than weak
acids
Ø Strong bases are better H+ acceptors than
weak bases
ü Strong acids have weak conjugate bases.
q Fully ionized, irreversible
ü Weak acids have strong conjugate bases.
q Weakly ionized, reversible

Conjugate acid Conjugate base
H2SO4 HSO4-
HBr Br- extremely
stong acids
weak bases
HCl Cl-
HNO3 NO3-
Base strength increasing

H3O+ H2O
Acid strength increasing
H2SO3 HSO3-
HSO4- SO42-
H3PO4 H2PO4-
HF F-
CH3COOH CH3COO-
H2S HS-
H2PO4- HPO42-
NH4+ NH3
HCO3- CO32-
H2O OH-
OH- O2-
H2 extremely H- strong base
CH4 weak acids CH3-
Ø Problem: Is the Conj acid. Conj. base
following aqueous H2SO4 HSO4-
HBr Br-
reaction product or
Base strength increasing

HCl Cl-
reactant favored?
Acid strength increasing

NH4+ + F- NH3 + HF HF F-
NH4+ NH3
ü Product favored if
leads to weaker acid
OH- O2-
ü Reactant favored if H2 H-
CH4 CH3-
otherwise
Molecular Structure and Acid Strength
Ø What makes a strong acid?
ü A weak H–A bond, so H+ can be easily
removed!
ü Consider the binary acids HF, HCl, HBr, HI.
larger acid strength

HX Bond Energy (kJ) Ka
smaller bond energy

HF weak acid 566 7 x 10-4
strong acids
HCl 431 1 x 107
HBr 366 1 x 108
HI 299 1 x 1010
ü Consider the Oxoacids: H-O-Z
ü Acid strength depends on the H-O bond
strength.
q If Z is electronegative it will pull e- to it
q Larger ENZ = weaker bond = stronger acid.
Name Formula Bonding ENZ Ka
hypochlorous acid HClO H-O-Cl 3.0 4 x 10-8
hypobromous acid HBrO H-O-Br 2.8 3 x 10-9
hypoiodous acid HIO H-O-I 2.5 2 x 10-11

ü Consider the Oxoacids: H-O-Z where Z is a
group of atoms
q If Z is more e- withdrawing = weaker bond
= stronger acid. More O atoms = more e-
withdrawing
Name Formula Bonding Ka
perchloric HClO4 H-O-ClO3 1 x 108
chloric acid HClO3 H-O-ClO2 1 x 103
chlorous acid HClO2 H-O-ClO 1 x 10-2
hypochlorous acid HClO H-O-Cl 4 x 10-8

Autoprotolysis
Ø Amphiprotic solvents undergo self-ionization,
or autoprotolysis, to form a pair of ionic
species.
Ø Other examples exhibiting autoprotolysis

Water’s Acid –Base Property
Ø Water is an amphiprotic solvent - it can donate
or accept a proton (act as acid or base)
ü Water acts as a base when an acid dissolves
in water:
HBr(aq) + H 2O(l) → H 3O+ (aq) + Br − (aq)
acid base acid base
ü But water acts as an acid for some bases:
€ H 2O(l) + NH 3 (aq) → NH 4 + (aq) + HO− (aq)

acid base acid base
Chemical Equilibrium
Ø Chemical equilibrium exists when two

opposing reactions occur simultaneously at the
same rate.
ü A chemical equilibrium is a reversible reaction
that the forward reaction rate is equal to the
reverse reaction rate.
Ø Chemical equilibria are dynamic equilibria.
ü Molecules are continually reacting, even
though the overall composition of the reaction
mixture does not change.
Chemical Equilibrium
Ø Equilibrium-constant expressions
ü are algebraic equations that describe the
concentration relationships among reactants
and products at equilibrium.
ü permit calculation of the error in an analysis
resulting from the quantity of unreacted analyte
that remains when equilibrium has been
reached.

Equilibrium Constant
Ø For the reaction:
→cC +dD
a A (g) + b B(g) ← (g) (g)
Ø The equilibrium constant:

c d
[C] [D]
KC =
[A]a [B]b
Ø Equilibrium constants are dimensionless
because they actually involve a thermodynamic
quantity called activity.
ü Activities are directly related to molarity
Ø If the direction of a reaction is reversed, the

new value of K is simply the reciprocal of the
original value of K.
Ø Example:
Ø The reverse reaction equilibrium constant:

Ø If a reaction can be expressed as the sum of two or
more reactions, the equilibrium constant for the
overall reaction is given by the product of the
equilibrium constants of the individual reactions.
ü If n reactions are added, the overall equilibrium
constant is the product of n individual equilibrium
constants.

Ø Sample Problem 1
ü Consider the following equilibria in aqueous
solution:
q Calculate the numerical value of the equilibrium constant

for the reaction AgCl(s) ! AgCl(aq)
q Calculate the concentartion of AgCl(aq) in equilibrium
with excess undissolved solid AgCl
q Find the numerical value of K for the reaction AgCl2- !
AgCl(s) + Cl-

Ø Large equilibrium constants indicate that most of
the reactants are converted to products.
Ø Small equilibrium constants indicate that only
small amounts of products are formed.

Equilibrium Constant in Analytical Chemistry

Le Chatelier’s Principle
Ø If a change of conditions (stress) is applied to
a system in equilibrium, the system responds
in the way that best tends to reduce the stress
in reaching a new state of equilibrium.
Ø Possible stresses to a system at equilibrium
ü Changes in concentration of reactants or
products.
ü Changes in pressure or volume (for gaseous
reactions)
ü Changes in temperature.
Le Chatelier’s Principle
Ø Sample Problem 2: Given the reaction below at
equilibrium in a closed container at 500oC. How
would the equilibrium be influenced by the
following?
ü Increasing reaction temperature

ü Decreasing reaction temperature
ü Increasing the the pressure by decreasing the volume
ü Increasing the concentration of H2
ü Decrease the concentration of NH3
Reaction Quotients
Ø The mass action expression or reaction quotient
has the symbol Q.
ü Q has the same form as Kc
Ø The major difference between Q and Kc is that
the concentrations used in Q are not necessarily
equilibrium values.
Ø Q will help us predict how the equilibrium will
respond to an applied stress.
ü To make this prediction we compare Q with Kc.

Reaction Quotients
Ø If
ü Qc < Kc system proceeds from left to right to reach
equilibrium
ü Qc = Kc the system is at equilibrium
ü Qc > Kc system proceeds from right to left to reach
equilibrium

Reaction Quotients
Ø Sample Problem 3:
ü The equilibrium constant for the reaction:
H2(g) + I2(g) ! 2HI(g)
is 49 at 450oC. If 0.22 mole of I2, 0.22 mole of H2,
and 0.66 mole of HI were put into an evacuated 1.00-
liter container, would the system be at equilibrium?
If not, what must occur to establish equilibrium?

Reaction Quotients
Ø Sample Problem 4:
ü An equilibrium mixture from the following reaction
was found to contain 0.20 mol/L of A, 0.30 mol/L of
B, and 0.30 mol/L of C. What is the value of Kc for
this reaction?
A(g) ! B(g) + C(g)
ü If the volume of the reaction vessel were suddenly
doubled while the temperature remained constant,
what would be the new equilibrium concentrations?
ü If the initial volume of the reaction vessel were
halved, while the temperature remains constant, what
will the new equilibrium concentrations be?
Acid-Base Equilibria
Ø The chemical equilibrium in solution that deals

quantitatively with acid and base ionization in
water
Ø Maybe
ü Autoionization of water
ü Ionization of Strong acids/Strong bases
ü Ionization of Weak acids/Strong bases
ü Ionization of Salts

Autoionization of Water
Ø Two water molecules can react to form ions
Ø Autoionization occurs:
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
Base Acid Acid Base
ü Strongly reactant favored… only small fraction

ionized
ü At 250C: K w = [H 3O ][ HO ]
+ −
ionization = (1.0x10 −7 )(1.0x10 −7 )

constant for
water
= 1.0x10 −14
Ø Kw (ion product constant), like all equilibrium
constants, is T-dependent.
Ø T = 25°C (77°F) is usually used as the
standard T.
T (°C) Kw
10 0.29 x 10-14
15 0.45 x 10-14
20 0.68 x 10-14
25 1.01 x 10-14
30 1.47 x 10-14
50 5.48 x 10-14

Ø H3O+ and OH- are present in all aqueous
solution
ü Neutral solution (pure H2O at 25°C:
[H3O+] = 10-7 M = [OH-]
ü Acidic solution:
[H3O+] > 10-7 M > [OH-]
ü Basic solution:
[H3O+] < 10-7 M < [OH-]

Ø Sample Problem: Calculate the hydronium and

hydroxide ion concentrations at 25°C in a 6.0
M aqueous sodium hydroxide solution.
Answer:
[H3O+] = 1.7 x 10-15 M

The pH and pOH scale
Ø A convenient way to express the acidity and

basicity of a solution is the pH and pOH scales.
Ø Acid/base concentration can vary over a very
large range. A logarithmic scale is more
convenient and easy to understand:
+ -
pH = -log[H 3O ] pOH = -log[HO ]
Ø At 25°C a neutral aqueous solution has:

pH = −log [1.0 x 10-7] = −(−7.00) = 7.00
€ €
Ø Acidic solutions:
pH < 7.00 (lower pH
= more acidic)
Ø Basic solutions:
pH > 7.00 (higher
pH = more basic)

Ø Kw may also be expressed in pKw:

ü Since Kw = [ H3O+ ][ OH- ] = 1.0 x 10-14
ü Taking the log of both sides:
−log(KW)= −log[H3O+] + (−log[OH-]) = −log(1.0 x 10-14)
pKw = pH + pOH = 14.00
Note: Valid in all aqueous solutions at 25°C:

acidic, neutral or basic

Ø Practice Problems:
ü Calculate the pH of a solution in which the
[H3O+] = 0.030 M.
ü The pH of a solution is 4.597. What is the
concentration of H3O+?
ü Calculate the [H3O+], pH, [OH-], and pOH for a
0.020 M HNO3 solution.
ü Given two aqueous solutions (25°C): Solution
A: [OH-] = 4.3 x 10-4 M, and Solution B: [H3O+]
= 7.5 x 10-9 M. Which has the higher pH? Which
is more acidic?
Measuring pH
Ø H3O+ concentrations can be

measured with an:
ü pH meter
q Fast and accurate and is the
preferred method
ü Acid-base indicator
q substance that changes color within a narrow pH
range
q Example: litmus paper, pH paper, indicator like
phenolphthalein
kadecastro-cruz
q cheap and convenient
52 Chemical Equilibria
Acid Ionization Constant
Ø When a weak acid (acetic acid) ionizes in water:
→
CH 3COOH + H 2 O ← H 3O + CH 3COO
+ -
Ø The equilibrium constant for this ionization is

expressed as:
!"H 3O+ #$ !"CH 3COO− #$
Kc =
[CH 3COOH ] [ H 2O]

Ø Recall that the activity of pure water is 1

!"H 3O+ #$ !"CH 3COO− #$
K c [ H 2 O] =
[CH 3COOH ]
!"H 3O+ #$ !"CH 3COO− #$
K ≈
[CH 3COOH ]
Ø This equilibrium constant is called acid
ionization constant, Ka
!"H 3O+ #$ !"CH 3COO− #$
Ka = = 1.8 ×10 −5
[CH 3COOH ]
Ø The acid ionization constant is used to report

the degree of ionization
ü Stronger acids have larger Ka (fully ionized)
ü Weak acid have small Ka values
ü For polyprotic acids, each H+ ionization has
a different Ka.
q The 1st proton is easiest to remove
q The 2nd is harder, etc.

Ø Phosphoric acid (H3PO4) is weak. It has three

acidic protons:
H3PO4(aq) + H2O(l) H3O+(aq) + H2PO4- (aq)
H+ is harder to remove
Ka decreasing
Ka = 7.5 x 10-3
H2PO4-(aq) + H2O(l) H3O+(aq) + HPO42- (aq)

Ka = 6.2 x 10-8
HPO42-(aq) + H2O(l) H3O+(aq) + PO43- (aq)

Ka = 3.6 x 10-13
Base Ionization Constant
Ø For a base in water:
B(aq) + H2O(l) BH+(aq) + OH-(aq)

Ø The base ionization constant, Kb, is:
!" BH + #$ !"HO− #$
Kc =
[ B]
Ø If the base is an anion:
A-(aq) + H2O(l) HA(aq) + OH-(aq)
[HA][OH-]
Kb =
[A-]
Acid & Base Ionization Constant
ü Write the equation for the ionization of the
weak acid HCN and the expression for its
ionization constant.
ü In a 0.12 M solution of a weak monoprotic
acid, HY, the acid is 5.0% ionized. Calculate
the ionization constant for the weak acid.
ü The pH of a 0.10 M solution of a weak
monoprotic acid, HA, is found to be 2.97.
What is the value for its ionization constant?
Weak Acid Ionization Problem
Ø Steps in Solving:
ü Identify the major species that can affect the pH.
ü In most cases, you can ignore the autoionization of water.
ü Ignore [OH-] because it is determined by [H+].
ü Use ICE to express the equilibrium concentrations in

terms of single unknown x.
ü Write Ka in terms of equilibrium concentrations.
Solve for x by the approximation method. If
approximation is not valid, solve for x exactly.
ü Calculate concentrations of all species and/or pH of
the solution.
Weak Acid & Base Ionization Problem
ü Calculate the concentrations of the various
species in 0.15 M acetic acid, CH3COOH,
solution. What is the percent ionization of
acetic acid
ü Calculate the concentrations of the species in
0.15 M hydrocyanic acid, HCN, solution.
ü Calculate the concentrations of the various
species in 0.15 M aqueous ammonia.

Weak Acid & Base Ionization Problem
ü The pH of an aqueous ammonia solution is
11.37. Calculate the molarity (original
concentration) of the aqueous ammonia
solution.
ü Calculate the concentration of all species in
0.100 M arsenic acid, H3AsO4, solution.

Ionization Constants of Conjugate Acid-Base Pairs
HA (aq) H+ (aq) + A- (aq) Ka
A- (aq) + H2O (l) OH- (aq) + HA (aq) Kb
H2O (l) H+ (aq) + OH- (aq) Kw
KaKb = Kw
Weak Acid and Its Conjugate Base
Kw Kw
Ka = Kb =
Kb Ka

Salts of Strong Bases and Acids
Ø Salts made from strong acids and strong
soluble bases form neutral aqueous solutions.
Ø Example: KNO3: made from potassium
hydroxide (KOH) and nitric acid (HNO3)
Ø The ions present in solution: KOH and HNO3

ü The KOH and HNO3 are present in equal amounts
and they are of equal strength
ü The solution is neutral
Salts of Strong Bases and Weak Acids
Ø Salts made from strong soluble bases and weak
acids hydrolyze to form basic solutions.
Ø Example: NaClO: made from sodium hydroxide
(NaOH) and hypochlorous acid (HClO)
Ø The ions present in solution: NaOH and HClO

ü Which is stronger, NaOH or HClO? The stronger species
dictates the pH of the solution.
ü The solution is therefore basic due of the stronger NaOH.

Ø Anions of weak acids (strong conjugate bases) react
with water to form hydroxide ions.
Ø The equilibrium constant for this reaction is called

hydrolysis constant:

Ø Derivation:
Ø Multiple this equation by 1 expressed as [H+]/ [H+]
and rearrange:

Ø Thus for hypochlorite ion the hydrolysis constant
is:

Ø Generalization: For the anion of any weak
monoprotic acid, the hydrolysis constant is:

Ø Example: Calculate the hydrolysis constants for the
following anions of weak acids.
Ø The fluoride ion, F-, the anion of hydrofluoric
acid, HF. For HF, Ka=7.2 x 10-4.

Ø Example: Calculate the hydrolysis constants for the
following anions of weak acids.
Ø The cyanide ion, CN-, the anion of hydrocyanic
acid, HCN. For HCN, Ka = 4.0 x 10-10.

Ø Example: Calculate [OH-], pH and percent
hydrolysis for the hypochlorite ion in 0.10 M
sodium hypochlorite, NaClO, solution. “Clorox”,
“Purex”, etc., are 5% sodium hypochlorite
solutions.
Ø Solution: Set up the equation for the hydrolysis and
the algebraic representations of the equilibrium
concentrations. [ClO-] will come from:

Ø Thus:
Ø The hydrolysis expression:

Ø Make and validate assumptions
Ø Solve for x:
Ø To compute for % hydrolysis:

Salts of Weak Bases and Strong Acids
Ø Salts made weak bases and strong acids hydrolyze
to form acidic solutions.
Ø Example: NH4Br: made from ammonia (NH3) and
hydrobromic acid (HBr)
Ø The ions present in solution: NH4OH and HBr

ü Which is stronger, NH4OH or HBr? The stronger species
dictates the pH of the solution.
ü The solution is therefore acidic due of the stronger HBr.

Ø Anions of weak base (strong conjugate acids) react
with water to form hydronium ions.
Ø The equilibrium constant for this reaction is called

hydrolysis constant:

Ø Derivation:
Ø Multiple this equation by 1 expressed as [OH-] [OH-]
and rearrange:

Ø Thus for ammonium ion the hydrolysis constant
is:

Ø Generalization: The reactions of anions of weak
monoprotic acids (from a salt) with water to form
free molecular base and H3O+.

Ø Example: Calculate [H+], pH, and percent
hydrolysis for the ammonium ion in 0.10 M
ammonium bromide, NH4Br, solution.
Ø Solution:
Ø Write down the hydrolysis reaction and set up the
expression.

Ø Solution:
Ø Substitute the algebraic expressions into the
hydrolysis constant, make assumptions.

Ø Solution:
Ø Do the algebra and solve for the value of x:

Ø Solution:
Ø Compute for the %hydrolysis of ammonium ion in
0.10 M NH4Br solution as follows:

Salts of Weak Bases and Weak Acids
Ø Salts made from weak acids and weak bases can
form neutral, acidic or basic aqueous
solutions.
Ø The pH of the solution depends on the relative
values of the ionization constant of the weak acids
and bases.
ü Salts of weak bases and weak acids for which
parent Kbase =Kacid make neutral solutions
ü Example: NH4CH3COO, made from aqueous
ammonia, NH3,and acetic acid, CH3COOH.
q Ka for acetic acid = Kb for ammonia = 1.8 x 10-5.

Ø Salts of weak bases and weak acids for which

parent Kbase > Kacid make basic solutions.
ü Example: Salts of weak ammonium hypochlorite,
NH4ClO, made from aqueous ammonia, NH3,and
hypochlorous acid, HClO.
ü Kb for NH3 = 1.8 x 10-5 > Ka for HClO = 3.5x10-8
q Since Kb > Ka ; the solution is basic

Ø Salts of weak bases and weak acids for which

parent Kbase < Kacid make acidic solutions.
ü Example: Salt of trimethylammonium fluoride,
(CH3)3NHF, made from trimethylamine, (CH3)3N,
and hydrofluoric acid acid, HF.
ü Kb for (CH3)3N = 7.4 x 10-5 < Ka for HF = 7.2 x 10-4
q Since Kb < Ka ; the solution is acidic

Common Ion Effect and Buffer Solution
Ø If a solution is made in which the same ion is

produced by two different compounds the
common ion effect is exhibited.
Ø Buffer solutions are solutions that resist
changes in pH when acids or bases are added
to them.
ü Buffering is due to the common ion effect.

Ø There are two common kinds of buffer

solutions:
ü Solutions made from a weak acid plus a
soluble ionic salt of the weak acid.
ü Solutions made from a weak base plus a
soluble ionic salt of the weak base

Ø Solutions made of weak acids plus a soluble
ionic salt of the weak acid
Ø One example of this type of buffer system is:
ü The weak acid - acetic acid CH3COOH
ü The soluble ionic salt - sodium acetate NaCH3COO
The weak acid reacts with bases.
⇓
→ CH COO - + H +
CH 3COOH ← 3
100%
Na + CH 3COO − "≈" "→ Na + + CH 3COO -
⇑
The salt anion (a base) reacts with acids.
Ø Sample Problem: Calculate the concentration
of H+ and the pH of a solution that is 0.15 M in
acetic acid and 0.15 M in sodium acetate.
NaCH 3COO "≈100%

"" → Na + + CH 3COO−
0.15 M 0.15 M 0.15 M
→ H + + CH COO-
CH 3COOH← 3
I : 0.15 M 0.15 M
C : −x M +x M +x M
E : (0.15 − x) M x M 0.15+x M
Ø Substitute the quantities determined in the
previous relationship into the ionization
expression.
!"H + #$ !"CH 3COO- #$ ( x ) ( 0.15 + x )
−5
Ka = = 1.8 ×10 =
[CH 3COOH ] (0.15 − x )
Ø Simplify the expression
(0.15 + x ) ≈ 0.15 and (0.15 − x ) ≈ 0.15

0.15x −5 x = 1.8 ×10 −5 M = #$H + %&
= 1.8 ×10
0.15 pH = 4.74
Ø Compare the acidity of a pure acetic acid
solution and the buffer described previously
Solution [H+] pH
0.15 M CH3COOH 1.6 x 10-3 2.80

0.15 M CH3COOH & 1.8 x 10-5
4.74
0.15 M NaCH3COO buffer
ü [H+] is 89 times greater in pure acetic acid than in

buffer solution.

Ø The general expression for the ionization of a
weak monoprotic acid is:
→ +
HA ← H + A −
Ø The generalized ionization constant expression

for a weak acid is:
!"H + #$!"A − #$
Ka =
[ HA]
ü If we solve the expression for [H+], this relationship
results: [ HA]
!"H + #$ = K a acid
!"A − #$
salt
ü By making the assumption that the concentrations
of the weak acid and the salt are reasonable, the
expression reduces to:
!"H + #$ = K a × [ acid ]
[salt ]
q This relationship is valid for buffers containing a weak
monoprotic acid and a soluble, ionic salt.
ü If the salt’s cation is not univalent the relationship

changes to:
!"H + #$ = K a × [ acid ]
n [salt ]
where n = charge on cation
ü Taking the logarithm of both sides and simple
rearrangement of this equation and application of
algebra yields the Henderson-Hasselbach
equation
! +#
log "H $ = log K a + log
[ acid ]
[salt ]
multiply by -1
! +#
− log "H $ = − log K a + log
[ salt ]
[acid ]
pH = pK a + log
[ salt ]
[acid ]
q The Henderson-Hasselbach equation is one method to
calculate the pH of a buffer given the concentrations of the
salt and acid. 94
kadecastro-cruz Chemical Equilibria
Buffer Solution: Weak Base + Salt of Weak Bases
Ø Buffers that contain a weak base plus the salt of

a weak base: ammonia + ammonium nitrate
NH 3 → +
+ H 2 O← NH 4 + OH -
≈100% + −
NH 4 NO3 $ $$ → NH + NO
4 3
&'NH +4 () &'OH − ()
−5
Kb = = 1.8 ×10
[ NH 3 ]

Ø Sample Problem: Calculate the concentration of

OH- and the pH of the solution that is 0.15 M in
aqueous ammonia, NH3, and 0.30 M in
ammonium nitrate, NH4NO3.
NH 4 NO3 "≈100%
"" → NH +4 + NO−3
0.30 M 0.30 M 0.30 M
NH 3 → +
+ H 2 O ← NH 4 + OH −
I : 0.15 M 0.30 M
C : −x M xM xM
E : (0.15 − x) M (0.30+x) M xM
Ø Substitute the quantities determined in the

previous relationship into the ionization
expression for ammonia.
!"NH +4 #$ !"OH − #$
Kb = = 1.8 ×10 −5
[ NH 3 ]
Kb =
( 0.30 + x ) ( x )
= 1.8 ×10 −5
(0.15 − x )
The simplifying assumption can be applied.
( 0.30 ) ( x ) x = 9.0 ×10 −6 M = #$OH − %&
Kb = = 1.8 ×10 −5
(0.15) pOH = 5.05 and pH = 8.95

Ø A comparison of the aqueous ammonia

concentration to that of the buffer described
above shows the buffering effect.
Solution [H+] pH
0.15 M NH3 1.6 x 10-3 11.20
0.15 M NH3 & 9.0 x 10-6

8.95
0.15 M NH4NO3 buffer
ü [OH-] in aqueous ammonia is 180 times greater

than in buffer solution.

Ø We can derive a general relationship for buffer

solutions that contain a weak base plus a salt
of a weak base similar to the acid buffer
relationship.
ü The general ionization equation for weak bases is:
:B + H 2 O →
← BH + + OH −
where B represents a weak base
ü The general form of the ionization expression is:
!"BH + #$!"OH − #$
Kb =
[ B]
ü Solving for the [OH-]
"#OH − $% = K b [ ]base
B
"#BH + $%
salt
ü For salts that have univalent ions:
"#OH − $% = K b × [ base ]
[salt ]
ü For salts that have divalent or trivalent ions:
"#OH − $% = K b × [ base ]
n [salt ]
where n = charge on anion
ü Simple rearrangement of this equation and
application of algebra yields the Henderson-
Hasselbach equation.
" −$
log #OH % = log K b + log
[ base]
[salt ]
multiply by -1
" −$
− log #OH % = − log K b + log
[ salt ]
[ base]
pOH = pK b + log
[ salt ]
[ base]
Buffering Action
Ø Sample Problem:
If 0.020 mole of gaseous HCl is added to 1.00
liter of a buffer solution that is 0.100 M in
aqueous ammonia and 0.200 M in ammonium
chloride, how much does the pH change?
Assume no volume change due to addition of
the HCl.

Buffering Action
ü Solution:
q Calculate the pH of the original buffer solution
!"OH - #$ = K b × [ NH 3 ]
[ NH 4Cl]
!"OH - #$ = 1.8 ×10 −5 × 0.10M
0.20M
!"OH - #$ = 9.0 ×10 −6 M
pOH = 5.05 pH = 8.95

Buffering Action
ü Solution:
q Calculate the concentration of all species after
the addition of the gaseous HCl.
v The HCl will react with some of the ammonia and
change the concentrations of the species.
v This is another limiting reactant problem.
HCl + NH 3 → NH 4 Cl
Initial 0.020 mol 0.100 mol 0.200 mol
Change - 0.020 mol - 0.020 mol + 0.020 mol
After rxn. 0 mol 0.080 mol 0.220 mol

Buffering Action
ü Solution:
q Calculate the concentration of all species after
the addition of the gaseous HCl.
0.080 mol
M NH3 = = 0.080M
1.0 L
0.220 mol
M NH 4Cl = = 0.220M
1.0 L

Buffering Action
ü Solution:
q Using the concentrations of the salt and base
and the Henderson-Hassselbach equation, the
pH can be calculated.
"#OH $% = K b ×
− [ NH 3 ]
[ NH 4Cl]
"#OH − $% = 1.8 ×10 −5 × 0.080M
0.220M
"#OH − $% = 6.5 ×10 −6 M
pOH = 5.19 pH = 8.81
Buffering Action
ü Solution:
q Finally, calculate the change in pH
ΔpH = pH new − pH original

ΔpH = 8.81 - 8.95
ΔpH = -0.14

Buffering Action
If 0.020 mole of NaOH is added to 1.00 liter of
solution that is 0.100 M in aqueous ammonia
and 0.200 M in ammonium chloride, how
much does the pH change? Assume no volume
change due to addition of the solid NaOH.
Answer: change in pH = 0.13

Buffering Action
Ø Summary of pH change in the two previous
problem:
Original Original Acid or base New
DpH
Solution pH added pH
1.00L of 0.020 mol
solution 9.08 +0.13
NaOH
containing
8.95
0.100 M NH3
and 0.200 0.020 mol HCl 8.81 -0.14
NH4Cl
ü Notice that the pH changes only slightly in each

case.
Preparation of Buffer Solutions
Ø Sample Problem: Calculate the concentration
of H+ and the pH of the solution prepared by
mixing 200 mL of 0.150 M acetic acid and 100
mL of 0.100 M sodium hydroxide solutions.
Ø Solution:
q Determine the amounts of acetic acid and sodium
hydroxide prior to the acid-base reaction.
0.15 mmol
? mmol CH 3COOH = 200 mL × = 30.0 mmol CH 3COOH
mL
0.100 mmol
? mmol NaOH = 100 mL × = 10.0 mmol NaOH
mL

Ø Solution:
q Sodium hydroxide and acetic acid react in a 1:1
mole ratio.
NaOH + CH 3COOH → Na CH 3COO + H 2O

Initial 10.0 mmol 30.0 mmol
Change -10.0 mmol -10.0 mmol + 10.0 mmol
After rxn. 0 20.0 mmol 10.0 mmol

Ø Solution:
q After the two solutions are mixed, the total volume
of the solution is 300 mL (100 mL of NaOH + 200
mL of acetic acid). Thus the concentrations of the
acid and base would be:
20.0 mmol
M CH 3COOH = = 0.0667 M CH 3COOH
300mL
10.0 mmol
M NaCH3COO = = 0.0333M NaCH 3COO
300mL

Ø Solution:
q Substitution of these values into the ionization
constant expression (or the Henderson-Hasselbach
equation) permits calculation of the pH.
#$H + %&#$CH 3COO− %&
K a = 1.8 ×10 −5 =
[CH 3COOH ]
#$H + %& = (1.8 ×10 −5
) (0.0667) −5
= 3.6 ×10 M
(0.0333)
pH = 4.44
Ø For biochemical situations, it is sometimes
important to prepare a buffer solution of a
given pH.
Ø Sample Problem: Calculate the number of moles
of solid ammonium chloride, NH4Cl, that must be
used to prepare 1.00 L of a buffer solution that is
0.10 M in aqueous ammonia, and that has a pH of
9.15.
q Because pH = 9.15, the pOH can be determined.
pOH=14.00-9.15=4.85
!"OH - #$ = 10 −4.85 = 1.4 ×10 −5 M
Ø Solution
q Establishing the equilibrium representation
NH 4Cl → NH +4 + Cl−
xM xM xM
NH 3 + H 2O →
← NH +4 + OH -
I : 0.10M xM
C : −1.4 ×10 −5 M +1.4 ×10 −5 M +1.4 ×10 −5 M
E : ( 0.10 −1.4 ×10 −5 ) M ( x +1.4 ×10 −5
) 1.4 ×10 −5 M

Ø Solution
q Substitute into the ionization constant expression
(or Henderson-Hasselbach equation) for aqueous
ammonia
!"NH +4 #$ !"OH − #$
Kb = = 1.8 ×10 −5
[ NH 3 ]
Kb =
(1.4 ×10 −5
+ x )(1.4 ×10 −5
)
( 0.10 −1.4 ×10 −5
)
Ø Solution
q Substitute into the ionization constant expression
(or Henderson-Hasselbach equation) for aqueous
ammonia
( )(
x 1.4 ×10 −5
)
Kb = = 1.8 ×10 −5
(0.10)
x = 0.13 M NH 4Cl= [ NH 4Cl]original
? g NH 4Cl 0.13 mol 53 g
= × = 6.9 g/L
L L mol

Solubility Equilibria
Ø Some ionic compounds are slightly water

soluble. Saturation occurs at low concentration.
AgCl(s) Ag+(aq) + Cl-(aq)

Ø The equilibrium constant for dissolution is
called the solubility product constant:
ü is the product of the concentrations of the
constituent ions, each raised to the power that
corresponds to the number of ions in one formula
unit of the compound.
Ksp = [Ag+][Cl-]
Ø Examples:
MgF2 (s) Mg2+ (aq) + 2F- (aq)

Ksp = [Mg2+][F-]2
Ag2CO3 (s) 2Ag+ (aq) + CO32- (aq)
Ksp = [Ag+]2[CO32-]
Ca3(PO4)2 (s) 3Ca2+ (aq) + 2PO43- (aq)
Ksp = [Ca2+]3[PO43-]2
ü What is the solubility product expression
for Ag2S?
ü Why is the solubility product expression for
calcium phosphate?
Answers:
2
K sp = !"Ag+ #$ !"S2− #$ = 1.0 ×10 −49
! # 2+ 3
! # 3− 2 −25
K sp = "Ca $ "PO $ = 1.0 ×10
4

Ø The same rules apply for compounds that have
more than two kinds of ions.
Ø One example of a compound that has more
than two kinds of ions is calcium ammonium
phosphate.
→ Ca 2+ + NH1+ + PO3−
CaNH 4 PO 4(s) ← (aq) 4(aq ) 4(aq )
$ 2+ & $ +& $ 3− &

K sp = %Ca ' %NH 4 ' %PO 4 '

Ø Molar solubility (mol/L) is the number of
moles of solute dissolved in 1 L of a saturated
solution.
Ø Solubility (g/L) is the number of grams of solute
dissolved in 1 L of a saturated solution.

Ø Sample Problem: One liter of saturated silver

chloride solution contains 0.00192 g of
dissolved AgCl at 25oC. Calculate the molar
solubility of, and Ksp for, AgCl.
Ø Solution:
ü Compute the molar solubility first
? mol AgCl 0.00192 g AgCl 1 mol AgCl
= ×
L L 143 g AgCl
−5 mol AgCl
= 1.34 ×10
L

Ø Solution:
ü Write the equilibrium expression for the
dissolution and solve the equation:
AgCl(s) ↔ Ag+ + Cl −
E: s s
s =1.34x10 -5 M
−
K sp = [Ag ][Cl ]
+
−5 −5
K sp = [1.34x10 ][1.34x10 ]
K sp = 1.80x10 −10
ü One liter of saturated calcium fluoride solution
contains 0.0167 gram of CaF2 at 25oC. Calculate
the molar solubility of, and Ksp for, CaF2.
q Answer: s= 2.14 x 10-4 M/Ksp = 3.92 x 10-11
ü Calculate the molar solubility of barium sulfate,
BaSO4, in pure water and the concentration of
barium and sulfate ions in saturated barium sulfate
at 25oC. For barium sulfate, Ksp= 1.1 x 10-10.
q Answer: [Ba2+] = [SO42-] = 1.0 x 10-5
M/solubility = 2.3 x 10-3 g/L

ü The solubility product constant for magnesium
hydroxide, Mg(OH)2, is 1.5 x 10-11. Calculate the
molar solubility of magnesium hydroxide and the
pH of a saturated magnesium hydroxide solution
at 25oC.
q Answer: s= 1.6 x 10-4 M/pH = 10.51

Solubility Equilibria: Common Ion Effect
ü Calculate the molar solubility of barium sulfate,
BaSO4, in 0.010 M sodium sulfate, Na2SO4,
solution at 25oC. Compare this to the solubility of
BaSO4 in pure water.
ü Solution:
q Write the equilibria expressions:
Na 2SO 4 !100%
!! → 2 Na + + SO 2−
4
0.010M 2(0.010M ) (0.010M )

→
BaSO 4(s) ← Ba (2+aq) + SO 2−
4(aq )
xM xM xM
ü Solution:
q Substitute the algebraic representations of the
concentrations into the Ksp expression and solve
for x.
K sp = !"Ba 2+ #$!"SO 2−
4 $
# = 1.1×10 −10
= ( x ) ( 0.010 + x )
(0.010 + x ) ≈ 0.010
0.010 x=1.1×10 -10
x = 1.1×10 −8 = molar solubility of BaSO 4
ü Solution:
q The molar solubility of BaSO4 in 0.010 M
Na2SO4 solution is 1.1 x 10-8 M.
q The molar solubility of BaSO4 in pure water is
1.0 x 10-5 M.
v BaSO4 is 900 times more soluble in pure water
than in 0.010 M sodium sulfate!
v The presence of a common ion decreases the
solubility of the salt
v Adding sodium sulfate to a solution is a fantastic
method to remove Ba2+ ions from solution!

References
ü Chang (2013). Chemistry, 10th ed.
ü Moore, Stanitski, Jurs (2008). Chemistry:
The Molecular Science
ü Whitten, Davis, Peck and Stanley (2013).
Chemistry, 9th ed.

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Chemical Equilibria

Dr. Kathlia A. De Castro-Cruz

kadecastro-cruz 2 Chemical Equilibria

ü Any substance which ionize in water to

kadecastro-cruz 3 Chemical Equilibria

kadecastro-cruz 4 Chemical Equilibria

NH3(g) + H2O(l) NH4+(aq) + OH-(aq)

kadecastro-cruz 5 Chemical Equilibria

kadecastro-cruz 6 Chemical Equilibria

ü Weak acids and bases do not fully ionize

kadecastro-cruz 8 Chemical Equilibria

kadecastro-cruz 9 Chemical Equilibria

a. HONH 2 + H 2O ↔ HONH 3 + + −OH

kadecastro-cruz 11 Chemical Equilibria

Ø Strong vs Weak Electrolytes

Alkaline and alkaline earth

Ø Strong vs Weak Electrolytes

Strong Electrolyte – 100% dissociation

Weak Electrolyte – not completely dissociated

CH3COOH CH3COO- (aq) + H+ (aq)

kadecastro-cruz 13 Chemical Equilibria

Ø Strong vs Weak Electrolytes

HNO3 (aq) + H2O (l) H3O+ (aq) + NO3- (aq)

HClO4 (aq) + H2O (l) H3O+ (aq) + ClO4- (aq)

H2SO4 (aq) + H2O (l) H3O+ (aq) + HSO4- (aq)

kadecastro-cruz 14 Chemical Equilibria

Ø Strong vs Weak Electrolytes

HF (aq) + H2O (l) H3O+ (aq) + F- (aq)

HNO2 (aq) + H2O (l) H3O+ (aq) + NO2- (aq)

HSO4- (aq) + H2O (l) H3O+ (aq) + SO42- (aq)

H2O (l) + H2O (l) H3O+ (aq) + OH- (aq)

kadecastro-cruz 15 Chemical Equilibria

Ø Strong vs Weak Electrolytes

kadecastro-cruz 16 Chemical Equilibria

Ø Strong vs Weak Electrolytes

F- (aq) + H2O (l) OH- (aq) + HF (aq)

NO2- (aq) + H2O (l) OH- (aq) + HNO2 (aq)

• H3O+ is the strongest acid that can exist in aqueous

Ø According to number of replaceable H+ and

kadecastro-cruz 18 Chemical Equilibria

Ø According to number of replaceable H+ and

kadecastro-cruz 19 Chemical Equilibria

Ø According to number of replaceable H+ and

kadecastro-cruz 20 Chemical Equilibria

kadecastro-cruz 21 Chemical Equilibria

Base strength increasing

Base strength increasing

Acid strength increasing

larger acid strength

smaller bond energy

HCl 431 1 x 107

HBr 366 1 x 108

kadecastro-cruz 25 Chemical Equilibria

kadecastro-cruz 26 Chemical Equilibria

kadecastro-cruz 27 Chemical Equilibria

ü But water acts as an acid for some bases:

€ H 2O(l) + NH 3 (aq) → NH 4 + (aq) + HO− (aq)

Ø Chemical equilibrium exists when two

kadecastro-cruz 30 Chemical Equilibria

Ø The equilibrium constant:

Ø If the direction of a reaction is reversed, the

Ø The reverse reaction equilibrium constant: