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5 - Acid and Base Equilibrium

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27 views127 pages

5 - Acid and Base Equilibrium

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謝迪
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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CCST 4153 – Basic Chemistry for Biological Sciences

Eig

Topic 5

Acid & Base


Equilibrium

(
Topic 5 - Overview
• Characteristics of Acids and Bases
• Brønsted–Lowry Acids and Bases
• Strengths of Acids and Bases
• Dissociation Constants for Acids and Bases
• Dissociation Constant of Water, Kw
• The pH Scale and Calculation
• Reactions of Acids and Bases
• Acid–Base Titration
• Buffers
Acids and Bases

A soft drink contains


T
phosphoric acid (H3PO4)
and carbonic acid
(H2CO3).

Learning Goal Describe and name acids and bases.


Arrhenius Acids

Arrhenius acids
• In 1887, Swedish chemist Svante Arrhenius was the first
to describe acids as substances that produce hydrogen
ions (H+) when they dissolve in water.

• are also electrolytes, because they produce H+ in water.


• have a sour taste.
test for acid
• turn blue litmus red.-

• corrode some metals.


Naming Acids

• Acids with a hydrogen ion (H+) and a nonmetal (or CN−) ion
are named with the prefix hydro and end with ic acid.

HCl(aq) hydrochloric acid

• Acids with a hydrogen ion (H+) and a polyatomic ion are


named by changing the end of the name of the polyatomic
ion from

ate to ic acid or ite to ous acid


ClO3− chlorate ClO2− chlorite
HClO3 chloric acid HClO2 chlorous acid
Names of Common Acids
H is remove and become negative

>
~

Study Check

Select the correct name for each of the following acids:

1. HBr A. bromic acid


B. bromous acid
D
C. hydrobromic acid

2. H2CO3 8
A. carbonic acid
B. hydrocarbonic acid
C. carbonous acid

3. HBrO2 A. bromic acid


B. hydrobromous acid
O
C. bromous acid
Arrhenius Bases

Arrhenius bases
• produce hydroxide ions (OH−)
in water.
• taste bitter or chalky.
• are also electrolytes, because
they produce hydroxide ions
(OH−) in water.
• feel soapy and slippery.
• turn litmus indicator paper
• blue and phenolphthalein
indicator pink.
Naming Bases

Typical Arrhenius bases are named as hydroxides.


NaOH sodium hydroxide
KOH potassium hydroxide
Ba(OH)2 barium hydroxide
Al(OH)3 aluminum hydroxide
Characteristics of Acids and Bases
Study Check

Match the formulas of acids and bases with their names.

i
1. HNO2 A. iodic acid
2. Ca(OH)2 B. sulfuric acid
3. H2SO4 C. sodium hydroxide
4. HIO3 D. nitrous acid
5. NaOH E. calcium hydroxide
Brønsted–Lowry Acids and Bases

In 1923, J. N. Brønsted in Denmark and T. M. Lowry in Great


Britain expanded the definition of acids and bases to include
bases that do not contain OH- ions.
Brønsted–Lowry Acids and Bases

According to the Brønsted–Lowry theory:


• an acid is a substance that donates H+.
• a base is a substance that accepts H+.

Learning Goal Identify conjugate acid–base pairs for


Brønsted–Lowry acids and bases.
NH3, a Brønsted–Lowry Base

In the reaction of ammonia and water,


• NH3 acts as the base that accepts H+.
• H2O acts as the acid that donates H+.

Because the nitrogen atom of NH3 has a stronger attraction


for H+ than oxygen, water acts as an acid by donating H+.
Study Check

In each of the following equations, identify the Brønsted–


Lowry acid and base in the reactants:
a
-

b
A. HNO3(aq) + H2O(l) H3O+(aq) + NO3−(aq)

B. HF(aq) + H2O(l) H3O+ (aq) + F−(aq)


a b
Conjugate Acid–Base Pairs

In any acid–base reaction, there are two conjugate acid–base


pairs.
• Each pair is related by the loss and gain of H+.
• One pair occurs in the forward direction.
• One pair occurs in the reverse direction.
Acid and conjugate base pair 1

HA + B A− + BH+

Base and conjugate acid pair 2


Conjugate Acid–Base Pairs

In this acid–base reaction,


• the first conjugate acid–base pair is HF, which donates H+ to
form its conjugate base, F−.
• the other conjugate acid–base pair is H2O, which accepts H+
to form its conjugate acid, H3O+.
• each pair is related by a loss and gain of H+.
Conjugate Acid–Base Pairs

In the reaction of NH3 and H2O,


• one conjugate acid–base pair is NH3/NH4+.
• the other conjugate acid–base pair is H2O/H3O+.

Core Chemistry Skill Identifying Conjugate Acid–Base Pairs


Study Check
(Remove the H)
It
already become conjugate base
-
1. Write the conjugate base for each of the following acids:
A. HBr
Br

B. H2S
HS-

C. H2CO3
HCOs-
Amphoteric Substances

Substances that can act as both acids and bases are


amphoteric or amphiprotic.

For water, the most common amphoteric substance, the


acidic or basic behavior depends on the other reactant.
• Water donates H+ when it reacts with a stronger base.
• Water accepts H+ when it reacts with a stronger acid.
Study Check

Identify the conjugate acid–base pairs in the following reaction:

.
b 1
HNO3(aq) + NH3(aq) NO3−(aq) + NH4+(aq)
Conjugate acid
loss H- > acid .

conjugate base
Study Check

Identify the sets that contain acid–base conjugate pairs.


1. HNO2, NO2 –
Answer: acid, conjugate base
2. H2CO3, CO32−
3. HCl, ClO4−
*
4. HS−, H2S base acid
, conjugate
5. NH3, NH4+ base ,
conjugate acid
Strengths of Acids and Bases

Weak acids only partially


dissociate in water.

Hydrofluoric acid, HF, is the


only halogen that forms a
weak acid.

Learning Goal Write equations for the dissociation of


strong and weak acids; identify the direction of reaction.
Strong and Weak Acids

A strong acid completely ionizes (100%) in aqueous


solutions.

HCl(g) + H2O(l) H3O+(aq) + Cl−(aq)

A weak acid dissociates only slightly in water to form a few


ions in aqueous solutions.

H2CO3(aq) + H2O(l) H3O+(aq) + HCO3− (aq)


Strong Acids

In water, the dissolved molecules


of HA, a strong acid,
• dissociate into ions 100%.
• produce large concentrations of
H3O+ and the anion (A−).

The strong acid HCl dissociates


completely into ions:
HCl(g) + H2O(l)
H3O+(aq) + Cl−(aq)
Weak Acids

In weak acids, only a few


molecules dissociate.
• Most of the weak acid
remains as the undissociated
(molecular) form of the acid.
• The concentrations of H3O+
and the anion (A−) are small.
H2CO3 is a weak acid:
H2CO3(aq) + H2O(l)
H3O+(aq) + HCO3−(aq)
Relative Strength of Acids and Bases
Strong and Weak Acid Dissociation

• In an HCl solution,
the strong acid HCl
dissociates 100% to
form H+ and Cl−.

• A solution of the
weak acid HC2H3O2
contains mostly
molecules of
HC2H3O2 and a few
ions of H+ and
C2H3O2−.
Strong and Weak Acid Dissociation

After dissociation in water,


(a) the strong acid HI has high concentrations of H3O+ and I–, and
(b) the weak acid HF has a high concentration of HF and low
concentrations of H 3O+ and F–.
Diprotic Acids: Carbonic Acid

• Some weak acids, such as carbonic acid, are diprotic acids


that have two H+, which dissociate one at a time.
H2CO3(aq) + H2O(l) H3O+(aq) + HCO3−(aq)
• Because HCO3− is also a weak acid, a second dissociation
can take place to produce another hydronium ion and the
carbonate ion, CO32−.
HCO3−(aq) + H2O(l) H3O+(aq) + CO32−(aq)
Diprotic Acids: Sulfuric Acid

• Some strong acids, such as sulfuric acid, are diprotic acids


that have two H+, which dissociate one at a time.

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

• Because HSO4− is a weak acid, a second dissociation can


take place to produce another H+ and the sulfate ion, SO42− .

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


Strong Bases

Strong bases as strong electrolytes


• are formed from metals of
Groups 1A (1) and 2A (2).
• include LiOH, NaOH, KOH,
Ba(OH)2, Sr(OH)2, and Ca(OH)2.
• dissociate completely in water.
KOH(s) K+(aq) + OH−(aq)
• are found in household products
used to remove grease and
unclog drains.
Weak Bases

Weak bases are weak electrolytes


• that are poor acceptors of H+ ions.
• produce very few ions in solution.
• include ammonia.

NH4+ (aq) + OH−(aq)


NH3(g) + H2O(l)
Ammonia Ammonium hydroxide
Strong and Weak Bases
Direction of Reaction

Strong acids have weak conjugate bases that do not readily


accept H+.

• As the strength of the acid decreases, the strength of its


conjugate base increases.

In any acid–base reaction, there are two acids and two bases.

• However, one acid is stronger than the other acid, and one
base is stronger than the other base.
• By comparing their relative strengths, we can determine
the direction of the reaction.
Direction of Reaction: H2SO4

Example 1
Sulfuric acid, H2SO4, is a strong acid that readily gives up H+
to water.

• The hydronium ion H3O+ produced is a weaker acid than


H2SO4.

• The conjugate base HSO 4− is a weaker base than water.


Direction of Reaction: CO32-

Example 2
The carbonate ion from carbonic acid, H2CO3, reacts with water.
• Water donates one H+ to carbonate, CO32− to form HCO3−
and OH−.
• From Table showing relative strength of acids and bases, we see
that HCO3− is a stronger acid than H2O.
• We also see that OH− is a stronger base than CO32−.

To reach equilibrium, the strong acid and strong base react in the
direction of the weaker acid and weaker base.
Study Check

Using relative strength of acids and bases, identify the


stronger acid in each pair.

A. HNO2 or H2S

B. HCO3− or HBr

C. H3PO4 or H3O+
Study Check

Does the equilibrium mixture of the following reaction contain


mostly reactants or products?
Reactants Products

Hints:

Check with Acids/Bases


strength table
Dissociation Constants for Acids and Bases
Dissociation of a Weak Acid

Because the dissociation of strong acids in water is


essentially complete, the reaction is not considered to be an
equilibrium process.

• Weak acids partially dissociate in water as the ion products


reach equilibrium with the undissociated weak acid
molecules.
• Formic acid is a weak acid that dissociates in water to form
hydronium ion, H3O+, and formate ion, CHO2−.

HCHO2 (aq) + H2O(l) H3O+(aq) + CHO2−(aq)


Writing Dissociation Constants

As with other dissociation expressions,


• An acid dissociation expression can be written for weak acids
that gives the ratio of the concentrations of products to the
reactants.
• the molar concentration of the products is divided by the molar
concentration of the reactants.
• water is a pure liquid with a constant concentration and is
omitted.
• the expression is called acid dissociation constant, Ka.

E.g. HCHO2 (aq) + H2O(l) H3O+(aq) + CHO2−(aq)


Writing Dissociation Constants

g. HCHO2 (aq) + H2O(l) H3O+(aq) + CHO2−(aq)

• The numerical value of the acid dissociation expression is


the acid dissociation constant, Ka.

• The value of the Ka for formic acid at 25 °C is determined


by experiment to be
Acid Dissociation Constant, Ka

When the value of the Ka


• is small, the equilibrium lies to the left, favoring the
reactants.
• is large, the equilibrium lies to the right, favoring the
products.

Weak acids have small Ka values, while strong acids


have very large Ka values.
Base Dissociation Constant, Kb

When the value of the base dissociation constant Kb,


• is small, the equilibrium lies to the left, favoring the reactants.
• is large, the equilibrium lies to the right, favoring the
products.

The stronger the base, the larger the Kb value.


CH3NH2(aq) + H2O(l) CH3NH3+(aq) + OH−(aq)

The concentration of water is omitted from the base


dissociation constant expression.
Weak Acids and Bases: Ka and Kb Values
Strength versus Equilibrium Position

Table summarizes the characteristics of acids and bases


in terms of strength and equilibrium position.
Study Check

Write the acid dissociation constant expression for nitrous acid,


HNO2.
Dissociation of Water

The equilibrium reached between the conjugate acid–base


pairs of water produces both H3O+ and OH−.
+ -
+ +

H2O(l) + H2O(l) H3O+(aq) + OH−(aq)

Learning Goal Use the water dissociation constant to


calculate the [H3O+] and [OH−] in an aqueous solution.
Dissociation Constant of Water, Kw

Water is amphoteric—it can act as an acid or a base.


In water,
• H+ is transferred from one H2O molecule to another.
• one water molecule acts as an acid, while another acts as
a base.
• equilibrium is reached between the conjugate acid–base
pairs.
Writing the Dissociation Constant, Kw

In the equation for the dissociation of water, there is both a


forward and a reverse reaction.
H2O(l) + H2O(l) H3O+(aq) + OH−(aq)
Base Acid Conjugate Conjugate
acid base

By omitting the constant concentration of pure water, we


can write the water dissociation expression, Kw.
Writing the Dissociation Constant, Kw

Experiments have determined that, in pure water, the


concentration of H3O+ and OH- at 25 °C are each 1.0 x 10-7 M.

Given That:

The numerical value of the water dissociation constant, Kw,


which is 1.0 x 10-14 at 25 °C.
Dissociation Constant, Kw

The ion product constant for water, Kw, is defined as


• the product of the concentrations of H3O+ and OH−.
• equal to 1.0  10−14 at 25 °C (the concentration units are
omitted).

When
• [H3O+] and [OH−] are equal, the solution is neutral.
• [H3O+] is greater than the [OH−], the solution is acidic.
• [OH−] is greater than the [H3O+], the solution is basic.
Using Kw to Calculate [H3O+] and [OH−]

• If we know the [H3O+] of a solution, we can use the


Kw to calculate the [OH−].

• If we know the [OH−] of a solution, we can use the


Kw to calculate the [H3O+].
Pure Water Is Neutral

In pure water, the ionization of water molecules produces


small but equal quantities of H3O+ and OH− ions.

[H3O+] = 1.0  107 M


[OH−] = 1.0  107 M

[H3O+] = [OH−]
Pure water is neutral.
Acidic Solutions

Adding an acid to pure water


• increases the [H3O+].
• causes the [H3O+] to exceed
1.0  10−7 M.
• decreases the [OH−].

[H3O+] > [OH−]


The solution is acidic.
Basic Solutions

Adding a base to pure water


• increases the [OH−]
• causes the [OH−] to exceed
1.0  10−7 M
• decreases the [H3O+]

[H3O+] < [OH−]


The solution is basic.
Comparison of [H3O+] and [OH−]
Neutral, Basic, and Acidic Solutions

Core Chemistry Skill Calculating [H3O+] and [OH−] in Solutions


Guide to Calculating [H3O+] and [OH–] in
Aqueous Solutions
Calculating [H3O+]

What is the [H3O+] of a solution if [OH−] is 5.0 × 10−8 M?

STEP 1 State the given and needed quantities.

ANALYZE Given Need Know


THE [OH−] = 5.0 × 10−8 M [H3O+] Kw = [H3O+][OH−]
PROBLEM = 1.0 × 10−14

STEP 2 Write the Kw for water and solve for the


unknown [H3O+].
Calculating [H3O+]

What is the [H3O+] of a solution if [OH−] is 5.0 × 10−8 M?

STEP 3 Substitute in the known [H3O+] or [OH−] and


calculate.

Because the [H3O+] of 2.0 × 10–7 M is larger than the


[OH−] of 5.0 × 10–8 M, the solution is acidic.
Study Check

If lemon juice has [H3O+] of 2.0 × 10–3 M, what is the [OH−] of


the solution?
A. 2.0 × 10−11 M
B. 5.0 × 10−11 M
C. 5.0 × 10−12 M
The pH Scale

The pH scale is used to


describe the acidity of
solutions.

A dipstick is used to
measure the pH of urine.

Learning Goal Calculate the pH from [H3O+]; given the


pH, calculate [H3O+] and [OH−] of a solution.
The pH Scale

The pH of a solution
• is used to indicate the acidity of a solution.
• has values that usually range from 0 to 14.
• is acidic when the values are less than 7.
• is neutral at a pH of 7.
• is basic when the values are greater than 7.
The pH Scale

The pH of a solution is commonly measured using

• a pH meter in the laboratory.


• pH paper, an indicator that turns specific colors at a
specific pH value.

The pH of a solution is found by comparing the colors of


indicator paper to a chart.
pH Measurement

The pH of a solution can be determined using


(a) a pH meter,
(b) pH paper, and
(c) indicators that turn different colors corresponding to
different pH values.
pH of Common Substances

On the pH scale,
values below 7.0
are acidic, a value
of 7.0 is neutral,
and values above
7.0 are basic.
Study Check

Identify each solution as acidic, basic, or neutral.

A. HCl with a pH = 1.5


B. pancreatic fluid, [H3O+] = 1  10−8 M
C. Sprite soft drink, pH = 3.0
D. pH = 7.0
E. [OH−] = 3  10−10 M
F. [H3O+ ] = 5  10−12
Calculating the pH of Solutions

The pH scale
• is a logarithmic scale that corresponds to the [H3O+] of
aqueous solutions.
• is the negative logarithm (base 10) of the [H3O+].
pH = −log[H3O+]

To calculate the pH, the negative powers of 10 in the molar


concentrations are converted to positive numbers.
If [H3O+] is 1.0  10−2 M,
pH = −log[1.0  10−2 ] = −(−2.00) = 2.00

Key Math Skill Calculating pH from [H3O+]


pH: Significant Figures

To determine the number of significant figures in the pH value,


• the number of decimal places in the pH value is the same
as the number of significant figures in the coefficient of
[H3O+].
• the number to the left of the decimal point in the pH value is
the power of 10.
pH Scale and [H3O+]

Because pH is a log scale,


• a change of one pH unit corresponds to a tenfold change
in [H3O+].
• pH decreases as the [H3O+] increases.

pH 2.00 is [H3O+] = 1.0  10−2 M


pH 3.00 is [H3O+] = 1.0  10−3 M
pH 4.00 is [H3O+] = 1.0  10−4 M
Guide to Calculating pH of Solutions

The pH of a solution is calculated from the [H3O+] by using the


log key in your calculator and changing the sign.
pH Calculation

Aspirin, which is acetylsalicylic acid, was the first nonsteroidal


anti-inflammatory drug used to alleviate pain and fever. If a
solution of aspirin has a [H3O+] = 1.7  10−3 M, what is the pH
of the solution?
pH Calculation

If a solution of aspirin has a [H3O+] = 1.7 ×10−3 M, what is


the pH of the solution?

STEP 1 State the given and needed quantities.

ANALYZE Given Need Know


THE [H3O+] = 1.7 × 10−3 M pH of solution pH = −log[H3O+]
PROBLEM
pH Calculation

If a solution of aspirin has a [H3O+] = 1.7 × 10−3 M, what is the


pH of the solution?

STEP 2 Enter the [H3O+] into the pH equation and


calculate.
pH = −log[H3O+] = −log[1.7 × 10−3]
Calculator Procedure:
log 1.7 EE or Exp 3 +/− =

Calculator Display: 2.769551079


pH Calculation

If a solution of aspirin has a [H3O+] = 1.7  10−3 M, what is the


pH of the solution?

STEP 3 Adjust the number of SFs on the right of the


decimal point.
Coefficient Power of ten
1.7  10–3
Two SFs Exact
pH = −log[1.7  10−3] = 2.77
Study Check

Find the pH of a solution with a [H3O+] of 4.0 × 10−5.


pH Values at 25°C

A Comparison of pH
Values at 25°C,

[H3O+], and [OH−]


Calculating [H3O+] from pH

Given the pH of a solution, we can reverse the calculation to


obtain the [H3O+].

• For whole number pH values, the negative pH value is the


power of 10 in the [H3O+] concentration.
[H3O+] = 10−pH
• For pH values that are not whole numbers, the calculation
requires the use of the 10x key, which is usually a 2nd
function key.

Key Math Skill Calculating [H3O+] from pH.


Guide to Calculating [H3O+] from pH
Calculating [H3O+] from pH

Determine the [H3O+] for a solution that has a pH


of 3.42.
Calculating [H3O+] from pH

Determine the [H3O+] for a solution that has a pH


of 3.42.

STEP 1 State the given and needed quantities.


ANALYZE Given Need Know
THE pH = 3.42 [H3O+] [H3O+] = 10−pH
PROBLEM
Calculating [H3O+] from pH

Determine the [H3O+] for a solution that has a pH


of 3.42.

STEP 2 Enter the pH value into the inverse log


equation and calculate.
Calculator Procedure:
2nd log 3.42 +/− =

Calculator Display: 3.801893963−04


Calculating [H3O+] from pH

Determine the [H3O+] for a solution that has a pH


of 3.42.

STEP 3 Adjust the SFs in the coefficient.

[H3O+] = 3.8 × 10−4 M


Two SFs
Study Check

Calculate [H3O+] for a urine sample, which has a pH of 7.5.


Reactions of Acids and Bases

Gastric acid contains


HCl and is produced by
parietal cells that line the
stomach.

When protein enters the


stomach, HCl is secreted
until the pH reaches 2,
the optimum pH for
digestion.

Learning Goal Write balanced equations for reactions of acids


with metals, carbonates, and bases.
Acids and Hydroxides: Neutralization

In a neutralization reaction,
• an acid reacts with a base to produce salt and water.
• the salt formed is the anion from the acid and the cation
from the base.

HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)


Acid Base Salt Water
Acids and Hydroxides: Neutralization

In neutralization reactions, one H+ always reacts with


one OH−.
• If we write the strong acid and strong base as ions,
HCl(aq) + NaCl(aq) NaOH(aq) + H2O(l)

we see that H+ reacts with OH− to form water, leaving the


ions Na+ and Cl− in solution:
H+(aq) + Cl−(aq) + Na+(aq) + OH−(aq)
Na+(aq) + Cl−(aq) + H2O(l)

• The overall reaction occurs as the H+ from the acid and OH−
from the base form water:
H+(aq) + OH−(aq) H2O(l) Net ionic equation
Guide to Balancing an Equation for
Neutralization
Balancing Neutralization Reactions

Write the balanced equation for the neutralization of solid


magnesium hydroxide and nitric acid.

STEP 1 Write the reactants and products.

Mg(OH)2(s) + HNO3(aq) salt + H2O(l)

STEP 2 Balance the H+ in the acid with the OH− in


the base.

Mg(OH)2(s) + 2HNO3(aq) salt + H2O(l)


Balancing Neutralization Reactions

Write the balanced equation for the neutralization of solid


magnesium hydroxide and nitric acid.

STEP 3 Balance the H2O with H+ and the OH−.

Mg(OH)2(s) + 2HNO3(aq) salt + 2H2O(l)

STEP 4 Write the salt from the remaining ions.

Mg(OH)2(s) + 2HNO3(aq) Mg(NO3)2(aq) + 2H2O(l)


Study Check

Write a balanced equation for the following reaction:


Mg(OH)2(s) + HBr(aq)
Study Check

Select the correct group of coefficients for each of the


following neutralization equations:
1. HCl(aq) + Al(OH)3(aq) AlCl3(aq) + H2O(l)
A. 1, 3, 3, 1 B. 3, 1, 1, 1 C. 3, 1, 1, 3

2. Ba(OH)2(aq) + H3PO4(aq) Ba3(PO4)2(s) + H2O(l)


A. 3, 2, 2, 2 B. 3, 2, 1, 6 C. 2, 3, 1, 6
Chemistry Link to Health: Antacids

Antacids are substances that


• are used to neutralize excess stomach acid.
• are made of aluminum hydroxide and magnesium
hydroxide mixtures.

These hydroxides are not


very soluble in water, so
the levels of available OH−
are not damaging to the
intestinal tract.
Chemistry Link to Health: Antacids

Basic Compounds in Antacids


Acid–Base Titration

The titration of an acid. A known volume of an acid is placed in


a flask with an indicator and titrated with a measured volume of
a base solution, such as NaOH, to the neutralization endpoint.

Learning Goal Calculate the molarity or volume of an acid or base


from titration information.
Acid–Base Titration

Titration
• is a laboratory procedure used to determine the molarity
of an acid.
• uses a base such as NaOH to neutralize a measured
volume of an acid.
• requires a few drops of an indicator such as
phenolphthalein to identify the endpoint.

Core Chemistry Skill Calculating Molarity or Volume of an Acid or


Base in a Titration
Acid–Base Titration

In the following
titration, a specific
volume of acidic Base 
solution is titrated to NaOH
the endpoint with a
known concentration
of NaOH.

Acid 
Solution
Indicator

The indicator phenolphthalein


• is added to identify the
endpoint.
• turns pink when the solution
is neutralized.
Endpoint of Titration

At the endpoint of the titration,


• the moles of base are equal to the
moles of acid in the solution.
• the concentration of the base is
known.
• the volume of the base used to
reach the endpoint is measured.
• the molarity of the acid is
calculated using the neutralization
equation for the reaction.
Guide to Calculating Boiling Point Elevation,
Freezing Point Lowering
Acid–Base Titration Calculations

What is the molarity of an HCl solution if 18.5 mL of


0.225 M NaOH is required to neutralize 0.0100 L of HCl?
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

STEP 1 State given and needed quantities and


concentrations.

ANALYZE Given Need Equation


THE 18.5 mL of molarity of HCl(aq) + NaOH(aq) 
PROBLEM 0.225 M NaOH HCl solution NaCl(aq) + H2O(l)
0.0100 L HCl
Acid–Base Titration Calculations

What is the molarity of an HCl solution if 18.5 mL of


0.225 M NaOH is required to neutralize 0.0100 L of HCl?
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

STEP 2 Write a plan to calculate molarity or volume.

mL NaOH Metric L NaOH moles of


factor Molarity
solution solution NaOH

moles of Mole–Mole moles of Divide by molarity of


NaOH factor HCl liters HCl solution
Acid–Base Titration Calculations

What is the molarity of an HCl solution if 18.5 mL of 0.225 M


NaOH is required to neutralize 0.0100 L of HCl?
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

STEP 3 State equalities and conversion factors including


concentration.
Acid–Base Titration Calculations

What is the molarity of an HCl solution if 18.5 mL of 0.225 M


NaOH is required to neutralize 0.0100 L of HCl?
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)

STEP 4 Set up the problem to calculate the needed


quantity.
Study Check

What is the molarity of an HCl solution if 25.5 mL of 0.438 M


NaOH is required to neutralize 0.0250 L of HCl?
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
Buffers

A buffer solution maintains the pH by neutralizing small amounts


of added acid or base.
An acid must be present to react with any OH− added, and a
base must be present to react with any H3O+ added.

Learning Goal Describe the role of buffers in maintaining


the pH of a solution; calculate the pH of a buffer.
Buffers

When an acid or a base


is added to water, the
pH changes drastically.
In a buffer solution,
the pH is maintained;
pH does not change
when acids or bases
are added.
How Buffers Work

Buffers work because


• they resist changes in pH from the addition of an acid or
a base.
• in the body, they absorb H3O+ or OH− from foods and
cellular processes to maintain pH.
• they are important in the proper functioning of cells
and blood.
• they maintain a pH close to 7.4 in blood.

A change in the pH of the blood affects the uptake of


oxygen and cellular processes.
Components of a Buffer

A buffer solution
• contains a combination of acid–base conjugate
pairs, a weak acid and a salt of its conjugate base,
such as
HC2H3O2(aq) and C2H3O2−(aq)

• has equal concentrations of a weak acid and its


salt.
How Buffers Work

For example:
In the buffer with acetic acid (HC2H3O2) and sodium acetate
(NaC2H3O2),

• As a weak acid, acetic acid dissociates slightly in water to


form H3O+ and a very small amount of C2H3O2-.

• The addition of its salt, sodium acetate, provides a much


larger concentration of acetate ion (C2H3O2-), which is
necessary for its buffering capability.
Function of a Weak Acid in a Buffer

If a small amount of base is added to this same buffer solution, it


is neutralized by the acetic acid, HC2H3O2, which shifts the
equilibrium in the direction of the products acetate ion and water.

The [HC2H3O2] decreases slightly and the [C2H3O22-] increases


slightly, but the [H3O+] and thus the pH of the solution are
maintained.
Function of Conjugate Base in a Buffer

When a small amount of acid is added, the additional H3O+


combines with the acetate ion, C2H3O2−, causing the equilibrium to
shift in the direction of the reactants, acetic acid and water.

There will be a slight decrease in the [C2H3O2−] and a slight increase


in the [HC2H3O2], but both the [H3O+] and pH are maintained
Working Buffers

The buffer described here consists of about equal concentrations of


acetic acid (HC2H3O2) and its conjugate base, acetate ion (C2H3O2−).
• Adding H3O+ to the buffer reacts with the salt, C2H3O2−, whereas
adding OH− neutralizes the acid HC2H3O2.
• The pH of the solution is maintained as long as the added
amounts of acid or base are small compared to the
concentrations of the buffer components.
Working Buffers

Buffer suitability
Calculating the pH of a Buffer

By rearranging the Ka expression to give [H3O+], we can obtain


the ratio of the acetic acid/acetate buffer and calculate the pH.

Core Chemistry Skill Calculating the pH of a Buffer


Calculating the pH of a Buffer

The Ka for acetic acid, HC2H3O2, is 1.8 × 10–5. What is the pH


of a buffer prepared with 1.0 M HC2H3O2 and 1.0 M C2H3O2−?

HC2H3O2(aq) + H2O(l) C2H3O2−(aq) + H3O+(aq)


Calculating the pH of a Buffer
Calculating the pH of a Buffer
Study check
Calculating the pH of a Buffer

Because Ka is a constant at a given temperature,


• the [H3O+] is determined by the [HC2H3O2]/[C2H3O 2−]
ratio.
• the addition of small amounts of either acid or base
changes the ratio of [HC2H3O2]/[C2H3O 2−] only
slightly.
• the changes in [H3O+] will be small and the pH will be
maintained.
• the addition of a large amount of acid or base may
exceed the buffering capacity of the system.
Buffers and pH Changes

Buffers can be prepared from conjugate acid–base


pairs such as

H2PO4−/HPO42− and HPO42−/PO43−, HCO3−/CO32−, or


NH4+/NH3.

The pH of the buffer solution will depend on the


conjugate acid–base pair chosen.
Buffers and pH Changes

Using a common phosphate buffer for biological specimens,


we can look at the effect of using different ratios of
[H2PO4−/HPO42−] on the [H3O+] and pH. The Ka of H2PO4−
is 6.2 × 10−8.

The equation and the [H3O+] are written as follows:


H2PO4−(aq) + H2O(l) H3O+(aq) + HPO42−(aq)
Buffers and pH Changes

To prepare a phosphate buffer with a pH close to the pH of a


biological sample, 7.4, we would choose concentrations that
are about equal, such as 1.0 M H2PO4- and 1.0 M HPO42-.
Buffers and pH Changes
Concept Map

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