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Lecture PowerPoint Slides

to accompany

CHEMISTRY
Human Activity,
Chemical Reactivity

Prepared by
Philip Elder, Ph.D.

Copyright 2015 by Nelson Education Limited 1


Chapter 14

Acid-Base Equilibria in
Aqueous Solution

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How Do You Like Your Acids:
Ionized or Un-ionized?

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How Do You Like Your Acids:
Ionized or Un-ionized?
Under pressure during exams, you have a
headache and swallow an aspirin tablet. A half
hour later, you are well enough to get back to
work.

What is the chemical compound in aspirin that


helped you? How did it go from your stomach to
your head?

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How Do You Like Your Acids:
Ionized or Un-ionized?
Most pharmaceutical drugs are transported to where
they are needed through the blood circulation system.
They can enter through direct injection, or through
absorption into the gastrointestinal tract walls (stomach
or intestine).
The proportion of a drug dose that makes its way into
the system and becomes available to do its job is called
its bioavailability
At the heart of bioavailability is the fact that most drugs
are weak acids.
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How Do You Like Your Acids:
Ionized or Un-ionized?
As weak acids, only some of the molecules are ionized
at any moment. Dissolved weak acids participate in
equilibrium reactions with water molecules.

HA(aq) + H2O() A(aq) + H3O(aq)

Aspirin consists of the chemical compound


acetylsalicylic acida carboxylic acid.

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How Do You Like Your Acids:
Ionized or Un-ionized?
Weak acids differ in how weak they are. The weaker the
acid, the lower the [A]/[HA] ratio in solution.
A chemists shorthand way of specifying the
concentration of H3O+(aq) ions is pH.
pH = log10[H3O+]
Aspirin is absorbed in the stomach where the low pH
maintains it in its uncharged protonated form.
In this chapter, the relationship between pH and the
ionization constant Ka will be discussed, as well as its
relationship with species present in solution.
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The Brnsted-Lowry Model of Acids
and Bases

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The Brnsted-Lowry Model of Acids
and Bases
Naturally Occurring Bases:

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The Brnsted-Lowry Model of Acids
and Bases
Biologically Produced Amine Bases:

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Common Acids and Bases and Their
Household Uses

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The Brnsted-Lowry Model of Acids
and Bases
Strong acids are strong electrolytes, in that they
fully ionize due to an acid-base reaction with water.

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The Brnsted-Lowry Model of Acids
and Bases
Weak acids are weak electrolytes, in that only some
molecules ionize due to an acid-base reaction with
water.

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The Brnsted-Lowry Model of Acids
and Bases
Characteristics of Acids, Bases, and Amphoteric
Species
Strong bases are strong electrolytes (e.g., NaOH).
Weak bases are weak electrolytes (e.g., ammonia,
acetate ions).
Monoprotic acids have molecules with only one
removable H+ ion (e.g., HF, HCl, HNO3, CH3COOH).
Polyprotic acids have more than one removable H+ ion
(e.g., H2SO4).
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The Brnsted-Lowry Model of Acids
and Bases
Polyprotic Acids:
Multiple steps of ionization, the first as a strong
acid, subsequent steps are weak.
Strong
H2SO4() + H2O() HSO4(aq) + H3O+(aq)
HSO4(aq) + H2O() Weak
SO42(aq) + H3O+(aq)

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The Brnsted-Lowry Model of Acids
and Bases
Species that can behave either as proton donors or
proton acceptors are said to be amphoteric.
Two species whose compositions differ by an H+ ion are
called a conjugate acid-base pair.

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Conjugate Acid-Base Pairs* in Some
Reactions in Aqueous Solution

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Water and the pH Scale
Water Self-Ionization and the Water Ionization
Constant (Kw)
At equilibrium Q = [H3O+][OH] = Kw
Kw = 1.0 1014 at 25C
The self-ionization reaction is endothermic, and Kw
increases with temperature.

Neutral: [H3O+] = [OH]


Acidic: [H3O+] > [OH]
Basic: [H3O+] < [OH]

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Water and the pH Scale
pHA Logarithmic Scale of Hydronium Ion
Concentrations
pH = log10[H3O+]
pOH = log10[OH]

In aqueous solutions at 25C, pH + pOH = 14.00.


Acidic solutions have pH < 7.0
Basic solutions: pH > 7.0

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Ex.
What is the [H3O+] and [OH-] in a 3.7 x 10-3
mol/L solution of HBr? pH?

Write eqs to show H2PO4- as an acid and as a


base.

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The Relationships Among pH, pOH,
[H3O+] and [OH] at 25C

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Relative Strengths of Weak Acids
and Bases
Ionization Constants of Weak Acids and Bases
Equilibrium constants for ionization of weak acids and
weak bases in aqueous solution are called ionization
constants, Ka and Kb. The larger the ionization
constant, the stronger the weak acid or base.
EXAMPLES:
HA(aq) + H2O() H3O+(aq) + A(aq) Q
H O A
3

K

HA a

B(aq) + H2O() BH+(aq) + OH(aq) Q


BH OH

K

B b

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Ka Values for Some Monoprotic
Weak Acids in Aqueous Solution

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Relative Strengths of Weak Acids
and Bases
Relative values of Kb for ammonia, methylamine,
and aniline indicate,
Methylamine is the strongest weak base;
Aniline is the weakest weak base.

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Relative Strengths of Weak Acids
and Bases
Relationship between Ka of an Acid and Kb of Its
Conjugate Base
The stronger a weak acid is (the larger Ka is), the weaker
its conjugate base (the smaller Kb is).
For any conjugate acid-base pair
Ka Kb = Kw
pKa + pKb = pKw (=14.00 at 25C)
Note: Acid (base) strengths may pKa log10 K a
be compared using a logarithmic
pKb log10 Kb
Scale.
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Ionization Constants for Some Acids
and Their Conjugate Bases at 25C

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Ex.
The Ka for benzoic acid (C6H5COOH) is 6.3 x 10-5.
What is the pKa?
The pKa of chloroacetic acid (ClCH2COOH) is
2.87. Is it a stronger or weaker acid than benzoic
acid?
What is the Kb for the benzoate ion (C6H5COO-)?

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Relative Strengths of Weak Acids
and Bases
Acid-Base Character of Aqueous Solutions of Salts
The pH of solutions of salts depends on whether their
cations and anions are acidic or basic.
Aquated cations that are conjugate acids of strong bases
are weak acids; they have no effect on solution pH (e.g.,
ions of Groups 1 and 2 of the periodic table).
Aquated anions that are conjugate bases of strong acids
are weak bases; they have no effect on solution pH (e.g.,
Cl and NO3).

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Relative Strengths of Weak Acids
and Bases
Influence of Some Aquated Ions on pH of Aqueous
Solution:

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Relative Strengths of Weak Acids
and Bases
The aqueous solutions of many metal cations are
acidic.
A pH measurement shows
that a solution of copper (II)
sulfate is acidic. Among the
common cations, Al3+, Fe3+ and
Cr3+ form the most acidic
solutions. Salts of Al3+ and Fe3+
are used by gardeners to make
soils more acidic.
e14.12 Explain the pH values of different salt solutions.
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Ex.
Which one(s) of the following salts will give an
aqueous soln that is basic?
NaNO3
NH4Cl
AlCl3
KF

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The Lewis Model of Acids and Bases
Lewis Acids and BasesElectron Pair Transfer
A Lewis base is a molecule or ion that donates a pair of
electrons to another atom to form a covalent bond.
A Lewis acid accepts a pair of electrons from another
atom in the formation of a covalent bond.
The product of bond formation between a Lewis acid
and a Lewis base is called an adduct.
The Lewis acid-base model includes species that are
Brnsted-Lowry acids and bases.

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The Lewis Model of Acids and Bases
Lewis Acids and BasesElectron Pair Transfer
EXAMPLES:

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The Lewis Model of Acids and Bases
Visualization of Reactive Sites of Organic Acids
and Bases
Electrostatic potential map models
Red regions indicates where the negative charge of
electrons exceeds the positive charge on the nuclei
(basic sites of molecules)
Blue regions indicates where there is net positive
charge (acidic sites of molecules)

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The Lewis Model of Acids and Bases
Electrostatic potential map portrayal of reactant
and product species in the reaction between an
acetic acid molecule and an hydroxide ion.

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Estimating Ka from Solute
Concentration and Measured pH
EXAMPLE: A 0.10 mol L1 aqueous solution of lactic acid
(CH3CHOHCOOH) at 25C has a pH of 2.43. What is the Ka
for lactic acid at this temperature?
STRATEGY:
We can calculate the Ka if we put the equilibrium
concentration of all species into the reaction quotient.
The pH of the solution tells us the equilibrium
concentration of H3O+ (aq) ions; the other species can
be determined using stoichiometry.

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Estimating Ka from Solute
Concentration and Measured pH
EXAMPLE: A 0.10 mol L1 aqueous solution of lactic acid
(CH3CHOHCOOH) at 25C has a pH of 2.43. What is the Ka
for lactic acid at this temperature?
CH3CHOHCOOH (aq) + H2O() CH3CHOHCOO(aq) + H3O+(aq)

[H3O+] = 10pH = 102.43 = 3.7 103 mol L1


So at equilibrium,
[CH3CHOHCOOH] = (0.10 3.7 103) mol L1
[H3O+] = 3.7 103 mol L1
[CH3CHOHCOO] = 3.7 103 mol L1
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Estimating Ka from Solute
Concentration and Measured pH
EXAMPLE: A 0.10 mol L-1 aqueous solution of lactic acid
(CH3CHOHCOOH) at 25C has a pH of 2.43. What is the Ka
for lactic acid at this temperature?
At equilibrium,
[CH3CHOHCOOH] = (0.10 3.7 103) mol L1
[H3O+] = 3.7 103 mol L1
[CH3CHOHCOO] = 3.7 103 mol L1

[CH3CHOHCOO][H3O+] (3.7 103)(3.7 103)


Q= = = 1.4 104 = K
(0.10 3.7 103)
a
[CH3CHOHCOOH]
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Equilibria in Aqueous Solutions of
Weak Acids or Bases
Equilibrium Concentrations, pH, and Percentage
Ionization from Ka
EXAMPLE: Calculate the pH of a 0.020 mol L1 solution of
benzoic acid (C6H5COOH) at 25C if Ka = 6.3 105 at this
temperature.
STRATEGY:
Designate that the concentration of the weak acid
increases by x mol L1 as equilibrium is reached. The
stoichiometry of the reaction equation allows us to
determine equilibrium concentrations.
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Equilibria in Aqueous Solutions of
Weak Acids or Bases
EXAMPLE: Calculate the pH of a 0.020 mol L1 solution of
benzoic acid (C6H5COOH) at 25C if Ka = 6.3 105 at this
temperature.
C6H5COOH(aq) + H2O() C6H5COO(aq) + H3O+(aq)

[C6H5COO][H3O+] (x)(x)
Q= = = 6.3 105 = Ka
[C6H5COOH] (0.020 x)
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Equilibria in Aqueous Solutions of
Weak Acids or Bases
EXAMPLE: Calculate the pH of a 0.020 mol L1 solution of
benzoic acid (C6H5COOH) at 25C if Ka = 6.3 105 at this
temperature.
[C6H5COO][H3O+] (x)(x)
Q= = = 6.3 105 = Ka
[C6H5COOH] (0.020 x)
Use the quadratic equation and solve for x = 0.0011 mol L1
[C6H5COOH] = (0.020 x) = 0.019 mol L1
[H3O+] = x = 0.0011 mol L1
[C6H5COO] = x = 0.0011 mol L1
x
pH = log10[H3O ] = 2.96
+ % ionized 100 5.5%
0.020
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Equilibria in Aqueous Solutions of
Weak Acids or Bases
Dependence of Percentage Ionization on Magnitude of Ka
For weak acid solutions of a given concentration and at
a given temperature, the smaller Ka is, the lesser the
percentage of the weak acid that ionizes.

Percentage Ionization of 0.1 mol L1 Solutions of Some Weak Acids:

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Equilibria in Aqueous Solutions of
Weak Acids or Bases
Dependence of Percentage Ionization on Solution
Concentration
At a given temperature, the more dilute the solution of
a weak acid is, the greater the percentage of it that
ionizes.
Percentage Ionization of Solutions of Propanoic Acid with Different
Concentrations:

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Equilibria in Aqueous Solutions of
Weak Acids or Bases
Effect of Common Ions on Percentage Ionization
The presence of common ions reduces the extent of
ionization of a weak acid. This is called the common ion
effect.
Before adding a common ion, the equilibrium
condition Q = Ka is satisfied.
After adding a common ion, Q > Ka.
Restoration of equilibrium would be achieved by net
reaction in the direction that reduces Q.

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Ex.
Calculate the pH and the % ionization in a 0.30
M aq soln of acetic acid (CH3COOH), and
compare this with the pH and the % ionization
of CH3COOH if this soln also contained 0.10 M
of the salt CH3COONa (sodium acetate).

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Equilibria in Aqueous Solutions of
Weak Acids or Bases
Aqueous Solutions of Weak Bases
For weak bases in aqueous solution, there is a
corresponding set of relationships to those that pertain
to solutions of weak acids.

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Equilibria in Aqueous Solutions of
Weak Acids or Bases
Solutions of Polyprotic Acids or Their Bases
More than one proton can be removed from molecules of
polyprotic acids in acid-base reactions.
H3PO4(aq) + H2O() H2PO4(aq) + H3O+(aq) Ka1 = 7.5 103
H2PO4(aq) + H2O() HPO42(aq) + H3O+(aq) Ka2 = 6.2 108
HPO42(aq) + H2O() PO43(aq) + H3O+(aq) Ka3 = 3.6 1013
In solutions of weak polyprotic acids with large differences
in the successive Ka values, the pH depends primarily on
the hydronium ions generated in the first ionization step.
A similar effect is observed for basic solutions.
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Ex.
What is the pH of a 0.10 M soln of oxalic acid
(H2C2O4) at 25 C? What are [H3O+] and
[HC2O4-]?

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Equilibria in Aqueous Solutions of
Weak Acids or Bases
Two Measures of Acidity of a Solution
The term Acidity can refer to either the pH of the
solution, or the amount of base needed to neutralize
the dissolved acid (its neutralizing capacity).
Reactions in aqueous solution between an acid and the
conjugate base of any weaker acid are product-favoured
and go to completion.
A base can react with all of the removable protons of
a weak acid (and not just the hydronium ions
present) at equilibrium.
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Speciation: Relative Concentrations
of Species
An important aspect of acid-base chemistry is how the
relative concentrations of a weak acid and its conjugate
base depend on the pH of a solution.
In the gold-mining industry, large amounts of sodium
cyanide are added to slurries of ore in water to dissolve
the gold and separate it from gangue.
Cyanides are poisonous, and the most lethal form of
cyanides is the gas hydrogen cyanide (HCN).
By controlling the pH, the concentration of HCN(aq) is
kept at a low enough level that workers are not at risk.
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Speciation: Relative Concentrations
of Species
Distribution between Acid and Base Species as pH
Is Changed
HCN(aq) + H2O() CN(aq) + H3O(aq) Ka = 4.0 1010

At equilibrium:
[CN][H3O+] [HCN] [H3O+]
Q= = Ka =
[HCN] [CN] Ka

The ratio of [HCN] to [CN] is directly proportional


to the concentration of H3O+ ions.
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Speciation: Relative Concentrations
of Species
Distribution between HCN(aq) and CN (aq) at
various pH values at 25C

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Speciation: Relative Concentrations
of Species
This speciation plot
shows the changing
distribution between
the HCN (aq) and
CN(aq) species as pH is
changed. At a given pH,
a point on the curve for
either species is its
percentage of the total
cyanide concentration.

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Speciation: Relative Concentrations
of Species
pH-dependent UV absorption peaks of HOCl (aq) and
OCl(aq) ions. Both the acid and its conjugate base absorb
ultraviolet radiation.

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Speciation: Relative Concentrations
of Species
A similar reasoning applies to the distribution between
any weak acid-conjugate base pair as pH is changed.
The generalized equation for weak acidconjugate base
equilibrium:
HA(aq) + H2O() A(aq) + H3O(aq)

[HA] [H3O+]
=
[A] Ka

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Speciation: Relative Concentrations
of Species
Acid-Base Speciation and Complexation with
Metal Ions
Complexation to metal cations by Lewis bases decreases
at low pH because of protonation of the bases,
occupying the bonding sites on the molecules or ions of
the bases.
The H3O+ ions effectively compete with metal ions in
solution for the Lewis basic molecules.

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Speciation: Relative Concentrations
of Species
Distribution among Species from Polyprotic Acids
Speciation between the conjugate acid-base pair of
each ionization step of a polyprotic acid simultaneously
obeys a relationship of the form:

[acid] [H3O+]
=
[base] Ka

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Speciation: Relative Concentrations
of Species
pH-Dependent Speciation of Amino Acids
All amino acids have a molecular structure commonly
portrayed as in the diagrams shown.

Each amino acid has a different R-group (see Table


14.10).
Amino acids never exist as portrayed above. For
example, at low pH they are protonated.
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pH-Dependent Speciation of Amino
Acids
pH-Dependent Glycine Speciation.
Glycine behaves as a weak
diprotic acid.

It has two ionization steps;


first the COOH proton is
removed, then the NH3+

At pH = 2.34 = pKa1 , [H2Gly+] = [HGly];


At pH = 9.60 = pKa2 , [HGly] = [Gly].
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Acid-Base Properties of Amino Acids
and Proteins
pH-Dependent Speciation of Glutamic acid.

[H3Glu+] = [H2Glu] at pH = pKa1 = 2.19


[H2Glu] = [HGlu] at pH = pKa2 = 4.25
[HGlu] = [Glu2] at pKa3 = 9.67

The isoelectric pH, at which the dominant species is the


zwitterion H2Glu with overall zero charge, is at pH = 3.2.
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Acid-Base Properties of Amino Acids
and Proteins
The pH-dependent speciation of amino acids is
as for other polyprotic acids.
The isoelectric pH for an amino acid is the pH at
which the species has a site with positive charge
and a site with a negative charge, but zero
overall chargecalled a zwitterion.
Carboxylic acid protons are more acidic (more
easily removed) than those on protonated amine
groups.
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Ex.
For phenylalanine, calculate the [acid]/[base]
ratio for the acid-base pair in soln at pH 7.4,
the pH of bodily fluids. Write the structure of
the dominant species at this pH, and give its
net charge.

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Controlling pH: Buffer Solutions
The pH meter indicates the
pH of water that contains a
trace of acid, as well as
some bromophenol blue
acid-base indicator.
(pH = 5.04)
The solution at left is a
buffer solution with a pH
of about 7, also with the
indicator.

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Controlling pH: Buffer Solutions
When 5 mL of 0.1 mol L1
HCl solution is added to
each solution, the pH of
the water drops by several
units (pH = 2.33, also
shown by the indicator
colour change).
The unchanged indicator
colour indicates that the
pH of the buffer solution
hardly changes.
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Controlling pH: Buffer Solutions
Composition and Mode of Operation of Buffers
Buffer solutions contain reagents that minimize the
change in pH when a strong acid or base is added.
They contain large amounts of both a weak acid and its
conjugate base, relative to the amounts of acid or base
that are added.
Buffer solutions function because the weak acid and
base are in equilibrium:
Added H3O+(aq) ions are mopped up by the conjugate base
Added OH(aq) ions are mopped up by the weak acid.
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Controlling pH: Buffer Solutions
Composition and Mode of Operation of Buffer
Solutions
Some Commonly Used Buffering Reagents:

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Controlling pH: Buffer Solutions
Quantitative Calculations of Buffer Solution pH
Consider the ratio of HA(aq) and A-(aq) ions depend on
concentration [A][H O+] 3
Q= = Ka
[HA]
Rearranging gives,
[HA]
[H3O+] = Ka
[A]
A logarithmic form is the Henderson-Hasselbalch
equation (obtained by taking the negative log of the
above): [A]
pH = pKa + log10
[HA]
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Quantitative Calculations of Buffer
Solution pH
EXAMPLE: What is the ph of an acetic acid/sodium
acetate buffer solution made with 0.350 mol of acetic acid
and 0.300 mol of sodium acetate dissolved in 500 mL of
solution?
n(CH3COOH) 0.350
[CH3COOH] = = = 0.700 mol L1
V 0.500
n(CH3COO) 0.300
[CH3COO] = = = 0.600 mol L1
V 0.500
At equilibrium,
[CH3COOH] = (0.700 x) mol L1 [CH3COO] = (0.600 x) mol L1
[H3O+] = mol L1
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Quantitative Calculations of Buffer
Solution pH
EXAMPLE: What is the pH of an acetic acid/sodium
acetate buffer solution made with 0.350 mol of acetic acid
and 0.300 mol of sodium acetate dissolved in 500 mL of
solution?
Using the concentrations of acetate and acetic acid:
[CH3COO][H3O+] (0.600 x)(x)
Q= = = Ka = 1.8 105
[CH3COOH] (0.700 x)

Using the quadratic equation, x = 2.1 105


[H3O+] = x = 2.1 105 mol L1, pH = 4.68
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Quantitative Calculations of Buffer
Solution pH
EXAMPLE: What is the pH of an acetic acid/sodium
acetate buffer solution made with 0.350 mol of acetic acid
and 0.300 mol of sodium acetate dissolved in 500 mL of
solution?
OR, substitute directly into: [HA]
+ [H3O ] = Ka
[A]

[CH3COOH] [0.700]
[H3O+] = Ka = (1.8 105) = 2.1 10-5 mol L1
[CH3COO] [0.600]

[H3O+] = 2.1 105 mol L1, pH = 4.68


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Controlling pH: Buffer Solutions
Design of a Buffer Solution of Specified pH
To design a buffer solution for a particular pH, choose a
weak acid with pKa within 1 unit of the target pH.
Calculate the [weak acid]/[conjugate base] ratio that
will adjust the solution pH to the target value.
Make a solution containing both the weak acid and its
conjugate base with the appropriate ratio.
Use amounts of the weak acid and conjugate base well
in excess of the amounts of strong acid or base that are
likely to be added.
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pH Change of Buffer Solutions
To calculate how much pH changes on addition of a
specified amount of H3O+(aq) to a buffer solution,
calculate
a) the amounts of weak acid and conjugate base in the
buffer solution,
b) the amount of H3O+(aq) added
c) the amount of acid that reacts and base that is
formed,
d) the new ratio n(acid)/n(base), and
e) the new pH using the above ratio, and Ka of HA(aq).

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Controlling pH: Buffer Solutions
Buffer capacity refers to the ability of a buffer
solution to minimize pH change upon addition
of strong acids or bases.
The more concentrated the weak acid and base
are in a solution, the higher the buffer capacity.
In addition,
(a) for a given amount of added strong acid or base,
the less is the pH change;
(b) the more strong acid or base can be added before
the solution loses its effectiveness.
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Ex.
Calculate the pH of a soln in which 2.00 g of
benzoic acid (C6H5COOH) and 2.00 g of sodium
benzoate (C6H5COONa) are dissolved in
enough water to make 1.00 L of soln at 25 C.

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Ex.
Calculate the pH of 0.500 L of a buffer soln
with 0.50 M formic acid and 0.70 M sodium
formate (a) before, and (b) after adding 10.0
mL of 1.0 M HCl soln.

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Acid-Base Titrations
The Methodology of Acid-Base Titrations
A titration is a method of quantitative analysis, based on a
reaction of known stoichiometry. It depends on finding the
volume of a solution containing the amount of acid (or
base) that reacts exactly with a known amount of base (or
acid).
EXAMPLE:
Determining the mass of oxalic acid in an impure sample by
titration with a strong base
H2C2O4(aq) + 2 OH(aq) C2O42(aq) + 2 H2O()

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Acid-Base Titrations
EXAMPLE:
Determining the mass of oxalic acid in an impure sample by
titration with a strong base.

H2C2O4(aq) + 2 OH(aq) C2O42(aq) + 2 H2O()

Using an accurately measured mass of the impure sample,


dissolve it in water, then add small increments of a
solution of sodium hydroxide of known concentration.
When the amount of added solution is just enough to
react with all of the oxalic acid present, the equivalence
point has been reached.
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Acid-Base Titrations
Strong AcidStrong Base Titrations
Change in pH as a solution of a strong acid is titrated
with a solution of a strong base.

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Acid-Base Titrations
Strong AcidStrong Base Titrations
At the equivalence point in titration of a solution of a
strong base into a solution of a strong acid, pH = 7.0.
The pH at any point prior to the equivalence point can
be calculated from the amount of unreacted acid.

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Weak AcidStrong Base Titrations

A CH3COOH solution is titrated with an NaOH solution. The pH is 2.87


at the start. When exactly half the acid has been reacted, pH = 4.74. At
the equivalence point, the solution is basic and the pH = 8.72.
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Acid-Base Titrations
Weak AcidStrong Base Titrations
At the equivalence point in titration of a solution of a
weak acid with a strong base, pH > 7, and can be
calculated using Kb of the conjugate base.
Prior to the equivalence point, the solution contains
both residual weak acid and some of its conjugate
base and is a buffer solution.
When exactly half the amount of strong base solution
needed to reach the equivalence point has been
added, pH = pKa of the weak acid.
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Acid-Base Titrations
Titration of Polyprotic Weak Acids with Strong Base
Solution
The curve for the titration of
a solution of oxalic acid with
a NaOH solution. The first
equivalence point occurs
when the most acidic H+ ion
of each H2C2O4 molecule has
been removed. The second
occurs after the second H+
ion has been removed.
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Acid-Base Titrations
Weak BaseStrong Acid Titrations
Titration of a weak base
solution (NH3) with a strong
acid solution (HCl). The pH at
the halfway point is equal to
the pKa for the weak acid
NH4+(aq) ions (9.26). At the
equivalence point, the pH of
the solution is due to the
weakly acidic NH4+(aq) ions,
and the pH is about 5.
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Acid-Base Titrations
Weak BaseStrong Acid Titrations
During titration of a solution of a weak base with a
solution of a strong acid, the conjugate acid of the
weak base is gradually formed, resulting in a buffer
solution.
When the volume of strong acid solution added is
exactly half that required for exact neutralization, pH =
pKa of the conjugate weak acid.

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Biochemical Acid-Base Speciation
Maintenance of pH in cellular fluids of living organisms
is vital, because enzyme activity is influenced by pH.
The main protection against harmful pH changes in
cells is provided by buffers.
In most cells, the pH is maintained between 6.9 and
7.4 through the action of phosphate (H2PO4/HPO42)
and carbonate (H2CO3/HCO3) buffers.
Just as increasing CO2(g) in the atmosphere causes
acidification of sea water, increased CO2(g)
concentration in the lungs can affect blood pH.

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pH of blood
pH of blood is buffered at 7.35. Important
equilibria in blood:
CO2 (g) CO2 (aq)
CO2 (aq) + H2O (l) H2CO3 (aq)
H2CO3 (aq) + H2O (l) HCO3- (aq) + H3O+ (aq) (pKa1 =
6.4)
HCO3- (aq) + H2O (l) CO32- (aq) + H3O+ (aq)

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Since pKa1 = 6.4, need a ratio of
[H2CO3]/[HCO3-] of 0.10/1 (implication on
buffer capacity?) to be at pH 7.35
For maintenance of metabolic processes, pH
of blood must be 7.35 to 7.45
Above = acidosis; below = alkalosis
Hyperventilating: can lead to alkalosis. Why
do you breathe into a paper bag, then?
Athletes can prevent metabolic acidosis, due
to lactic acid build-up by doing what prior to
their event? Copyright 2014 by Nelson Education Limited 87
Buffered products
Shampoo (pH 5 to 8). Marketing: pH balanced.
Baby lotion (pH 6) antimicrobial effect.
Alcohol production to prevent spoilage.
Milk (pH 6.7)

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