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Acids and Bases To Buffers 2023

Here are the answers: a) [H+] = 2.0 x 10-5 > 1.0 x 10-7. Therefore, the solution is acidic. b) [OH-] = 3.0 x 10-9 < 1.0 x 10-7. Therefore, the solution is acidic. c) [OH-] = 1.0 x 10-7. At this point [H+] would also equal 1.0 x 10-7. Therefore, the solution is neutral. 2. Calculate the [H+] if [OH-] = 5.0 x 10-11 Kw = [H+][OH-] 1.0 x 10-14 =
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0% found this document useful (0 votes)
22 views86 pages

Acids and Bases To Buffers 2023

Here are the answers: a) [H+] = 2.0 x 10-5 > 1.0 x 10-7. Therefore, the solution is acidic. b) [OH-] = 3.0 x 10-9 < 1.0 x 10-7. Therefore, the solution is acidic. c) [OH-] = 1.0 x 10-7. At this point [H+] would also equal 1.0 x 10-7. Therefore, the solution is neutral. 2. Calculate the [H+] if [OH-] = 5.0 x 10-11 Kw = [H+][OH-] 1.0 x 10-14 =
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ACIDS AND

BASES
BIOCHEMISTRY
Acids and bases play
an indispensable role
in academic, research
and many consumer
products.
PROPERTIES OF ACID AND
BASES
 Acids have sour taste, e.g. citrus acid in lemon juice

 Bases have bitter taste and feel slippery, e.g. soap

 Acids and Bases cause certain dyes to change color


 Acid turn blue litmus paper to red (BRA)

 Base turn red litmus paper to blue (RBB)

 When acids and base reacts each cancels the properties of the other
in a process called neutralization.
ACIDS AND BASES

❑ Acid - come from the latin word “acidus” meaning sour or


tart
❑ Base - come from the old English word which means to
bring low
❑ When bases are added with acids, they lower the amount of
acids and their characteristic properties disappear
altogether
❑ Most acids and base reactions involves water as a product
THREE DEFINITIONS OF ACIDS AND BASES

01 Arrhenius Definition
02 Brønsted-Lowry Definition
Acid: Reactant that donates proton [H+] in a
Acid: Substance that increases [H3O+] in solution reaction.

Base: Substance that increases [OH-] in solution Base: Reactant that accepts proton [H+] in a
reaction

03 Lewis Definition
(in the formation of covalent bonds)
Acid: electron pair acceptor.

Base: electron pair donor.


ARRHENIUS ACIDS AND
BASES
Svante Arrhenius, a Swedish chemist, 1880 defined:
 Acids are substances, when dissolved in water,
increases [H +]
Example: HCl gas, highly soluble in water
𝑯𝟐 𝑶
HCl ⟶ H+ (aq) + Cl- (aq)

In aqueous solution, HCl is hydrochloric acid


(concentrated sol’n = 12M)

 Bases are substances that, when dissolved in water,


increase [OH -]
𝑯𝟐 𝑶
NaOH ⟶ Na+ (aq) + OH- (aq)

 Limitations: Arrhenius concept of acid and bases are


restricted to aqueous solutions.
BRØNSTED-LOWRY
ACIDS AND BASES
BRØNSTED-LOWRY ACIDS AND BASES
 Based on the fact that the acid-base reactions involve the transfer of H+ ions from
one substance to another
• An H+ ion is simply a proton with no surrounding valence electrons
• H+ interacts strongly with nonbonding electron pairs of water molecules to form hydrated
hydrogen ions.

▪ Chemist use H + (aq) and H 3O + (aq) interchangeably to represent the same thing (the hydrated proton that
is responsible for the characteristic properties of water solutions in acid.)

▪ The H + ion is often used for simplicity and convenience though H 3O + (aq) is closer to reality.
BRØNSTED-LOWRY ACIDS AND BASES
Bronsted-Lowry Acid

A substance (molecule or
ion) that can transfer a
proton to another
substance

Bronsted-Lowry Base

A substance that can ▪ NH3 is a BL base, it accepts a proton from H 2O


accept proton ▪ An Arrhenius base, it increase [OH -]
CONJUGATE ACID-BASE PAIR

▪ An acid and a base which differ only by


the presence or absence of a
proton are called a conjugate acid-base
pair.

▪ Every acid has a conjugate base formed


by the removal of proton from the acid.

▪ Every base has a conjugate acid formed


by the addition of proton to the base.
CONJUGATE ACID-BASE PAIR
CONJUGATE ACID-BASE PAIR
LEWIS ACID-BASE DEFINITION
G.N Lewis concept of acid and bases emphasizes the shared electron pair rather
that the proton. In Lewis concept:

An acid is an electron-pair A base is an electron-pair


acceptor donor.

In Bronsted-Lowry concept:

An acid is a proton donor A base is a proton acceptor

The concept greatly increase the number of species that can be considered acids (not
only H+) and more general than Bronsted-Lowry concept.
LEWIS ACID-BASE
RELATIVE STRENGTH OF ACID AND BASE
• The stronger the acid, the weaker its conjugate base
• The stronger the base, the weaker its conjugate acid

Strong acids:
• Those that completely transfer their protons to H 2O
leaving no undissociated molecules in solution.
• Their conjugate bases have negligible tendency to be
protonated in aqueous solution.

Example:
The extent of dissociation for strong acids.

Strong acid: HA(g or l) + H2O(l) H3O+(aq) + A-(aq)


STRONG ACID
• Completely ionized in aqueous solution
• Strong electrolytes
• Examples: HCl, HBr, HI, HNO3, HClO4, and H2SO4

HCl→ H+ + Cl-
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)

H+ is a shorthand for H3O+.


STRONG BASE
• completely ionized in aqueous solution
• Strong electrolytes
• Examples: LiOH, NaOH, KOH, Ca(OH)2, and Ba(OH)2
H2O
NaOH (s) Na+ (aq) + OH- (aq)
H2O
KOH (s) K+ (aq) + OH- (aq)
H2O
Ba(OH)2 (s) Ba2+ (aq) + 2OH- (aq)
WEAK ACIDS AND BASES
• incompletely ionized in aqueous solution
• Examples: carboxylic acids, such as acetic acid, are weak acids
The extent of dissociation for weak acids.

Weak acid: HA(aq) + H2O(l) H3O+(aq) + A-(aq)


RELATIVE STRENGTH OF ACIDS AND BASES

WEAK ACIDS
•Those that only partly dissociate in aqueous solution and exist in solution as a mixture of acid
molecules and component ions at equilibrium.

Example:

•Their conjugate bases are weak bases, showing a slight ability to remove protons from H2O to form
OH- in.

Example:
Acids and
Bases ranked
byAcids
strength
and
Bases ranked
by strength
• The position of equilibrium of any chemical reaction is given by its equilibrium constant.
For the general reaction,

• An equilibrium constant can be defined in terms of concentrations of reactants (A and B)


and products (C and D) present at equilibrium :

𝑪 [𝑫] Strictly speaking, the bracketed


Keq= terms represent molar activity, rather
𝑨 [𝑩] than molar concentration.

• The equilibrium constant is fixed and characteristic for any given chemical reaction at a
specific temperature. It defines the composition of the final equilibrium mixture of that
reaction, irrespective of the starting amounts of reactants and products. Conversely, one
can calculate the equilibrium constant for a given reaction at a given temperature, if the
equilibrium concentrations of all its reactants and products are known.
Weak acid has Ka < 1 which leads to small [H3O+]
ACID STRENGTH
AUTOIONIZATION OF WATER
Water (H2O)
• An amphoteric substance that act as either Bronsted-Lowry acid or Bronsted-Lowry
base.

In the presence of an acid, H 2O acts as a In the presence of a base, H 2O acts as a


proton acceptor proton donor

• Water molecules can donate a proton to another water molecule

Note: No individual molecule remains ionized for long, the reactions are rapid in both directions; at room
temperature, only about 1 out of 103 molecules is ionized at a given instant thus pure water consist almost
entirely H2O molecules.
ION-PRODUCT OF WATER

At equilibrium:
[𝑯𝟑 𝑶+ ] [𝑶𝑯− ]
𝑲𝒄 = For pure water, [H 2O]≈ constant
[𝑯𝟐 𝑶]𝟐

𝑲𝒄 [𝑯𝟐 𝑶]𝟐 = 𝑲𝑾 = [H3O+][OH-] Kw = ion product constant for H 2O


At 25oC, 𝑲𝒘 = [H3O+] [OH-] = 1.0 x 10 -14 (for pure water and dilute aqueous solutions)

A solution for which Is said to be


[H+]=[OH-] neutral
[H+]>[OH-] acidic
[H+]<[OH-] basic
ION-PRODUCT OF WATER
For a neutral solution, [H+]=[OH-]

At 25oC, 𝑲𝒘 = [H3O+] [OH -] = 1.0 x 10 -14


[H3O+] [OH -] = 1.0 x 10 -14
[H3O+]2 = 1.0 x 10 -14
[H3O+] = 1.0 x 10−14 = 1.0 x 10 -7
Thus, [H+]= 1.0 x 10 -7 and [OH -]= 1.0 x 10 -7

Therefore,
A solution with [H+] > 1.0 x 10 -7 is acidic
A solution with [H+] < 1.0 x 10 -7 is basic
AA + BB cC + dD

K = [C]c [D] d
a b
[A] [B]

[ ] means molarity concentration


Molarity = M= mol/L

The larger the Ka, the more products are formed (forward reaction is
favored.)
The Ion-Product of Water
Sample Exercises
1. Indicate whether each of the following solutions is neutral, acidic or basic
a. [H+] = 2.0 x 10 -5 b.[OH-] = 3.0 x 10 -9 c. [OH-] = 1.0 x 10 -7

1. Calculate the concentration of H +(aq) in a solution in which


a. [OH-] = 0.10 M
b. [OH -] = 2.0 x 10 -9

1. Calculate the concentration of OH -(aq) in a solution in which?


a. [H+] = 2.0 x 10 -6
b. [H+] = [OH-]
c. [H+] = 100 x [OH -]
The pH Scale
• Soren Sorensen, a biochemist at Carlsberg Brewery in Copenhagen, proposed an
alternative method of specifying the acidity of a solution.

• Defined a term called pH for “power of hydrogen ion”

pH = -log [H+] or pH = -log [H3O+]

for neutral solution, [H+] = 1.0 x 10-7

pH = -log 1.0 x 10-7


pH = 7.00

A solution with Is
pH = 7.00 neutral
pH >7.00 basic
Ph < 7.00 acidic
The pH Scale
• pH (short for “potential of hydrogen”) is a symbol and denotes the relative
concentration of hydrogen ions in a solution.

• pH values extend from O to 14; the lower the value, the higher the acidity or the
more hydrogen ions the solution contains.

• Water at 25 °C has a concentration of H ion of 10 -7; the pH, therefore, is 7.

• The number of hydrogen ions present in a solution is a measure of the acidity of the
solution. All acids do not ionize completely when dissolved in water, i.e., all the molecules
of acid do not ionize and exist in the solution as electrically-charged particles. The
hydrogen ion concentration is a measure, therefore, of the amount of dissociated acid
rather than of the amount of acid present.
The pH Scale
Note: pH decreases as [H+] increases. Therefore, at 25 oC log K w = -log 1.0 x 10 -14

[H+], M [OH -], M pH Solution type


>1.0 x 10 -7 <1.0 x 10 -7 <7.00 acidic
=1.0 x 10 -7 =1.0 x 10 -7 =7.00 Neutral
<1.0 x 10 -7 >1.0 x 10 -7 >7.00 Basic

Sample Exercises
1. In a sample of lemon juice, [H+]=3.8 x 10 -4 M, what is its pH?
2. A common available window-cleaning solution has [H +]=5.3 x 10 -9 M, what is its pH?
3. A sample of freshly prepared apple juice has a pH of 3.76, calculate its [H +].
4. A solution formed by dissolving an antiacid tablet has a pH of 9.18, calculate its [H +].
The pH Scale
pOH = -log [OH-] : pKw = - log Kw since Kw =[H+] [OH -]

pKw = pH + pOH at 25 oC K w = -log 1.0 x 10 -14


pKw = -log 1.0 x 10 -14 = 14.00 → pH + pOH =14.00

pKa = -log Ka pKb = -log Kb

Measuring pH
1. Using dyes (litmus paper) or acid-base indicators, but this method is less precise
2. Using pH meter, this is method is quick and accurate
Strong Acids and Bases
• Strong electrolytes are 100% ionized in solution and exists in aqueous solution entirely as
ions.
Strong acids Strong bases

Group 1A hydroxides,
LiOH, NaOH, KOH, RbOH, CsOH
HCl. HBr, HI, HClO 3, HClO 4, HNO 3,
H 2SO 4
Heavy Group II metal hydroxides
Ca(OH) 2, Sr(OH) 2, Ba(OH) 2

** in aqueous solution of strong acid, the acid is normally the only significant source of ions, that is [H+]=acid
Strong Bases

[OH-] = base
Sample Exercise

1. What is the pH of a 0.011 M solution of Ca(OH) 2?


2. What is the concentration of a solution of KOH for which the pH is 11.89?
Note: For extremely dilute solutions, if the concentration of the acid is 10 -6 M or less, we will take
into consideration the H+ ions that result from the autoionization of water.

[H+] solution = [H +] acid + [H +] water


Example: What is the pH of 1.0 x 10 -8 M solution?
Similarly for extremely dilute solutions of bases
[OH -] solution = [OH -] base + [OH -] water
Example: What is the pH of a NaOH solution with a conc of 8.0 x 10 -8 M?
Problems
• An aqueous solution contain 0.10 M NaOH. This solution can be, acid, base or neutral? Prove.

• A neutralization between NH4OH and HBr will form?


a. NH4Br and H2O
b. NH4O and H2Br
c. BrOH and NH3
Problems
• An aqueous solution contain 0.10 M NaOH. This solution can be, acid, base or neutral? Prove.
• A neutralization between NH4OH and HBr will form?
a. NH4Br and H2O
b. NH4O and H2Br
c. BrOH and NH3
• Nitric acid is a strong acid, this means that?
• What is the pH of an aqueous solution in which, [H+]=0.0025M
• What is the concentration of hydronium ion at 25oC with pH=4.282
• What is the pH of an aqueous solution that contains 3.98 x 10-9M H+?
• For the reaction between HI and water tell what is the conjugate acid and base.
Problems
• An aqueous solution contain 0.10 M NaOH. This solution can be, acid, base or neutral? Prove.
• A neutralization between NH4OH and HBr will form?
a. NH4Br and H2O
b. NH4O and H2Br
c. BrOH and NH3
• Nitric acid is a strong acid, this means that?
• What is the pH of an aqueous solution in which, [H+]=0.0025M
• What is the concentration of hydronium ion at 25oC with pH=4.282
• What is the pH of an aqueous solution that contains 3.98 x 10-9M H+?
• For the reaction between HI and water tell what is the conjugate acid and base.
Weak Acids
• Only partially ionized in aqueous solution such that dissolved molecules exist in
equilibrium with their ions in solution.
• The extent of ionization for a weak acid (WA) is expressed by the equilibrium constant
for the ionization reaction
For a general weak acid, HX

[𝑯 𝟑 𝑶+ ] [𝑿− ]
𝑲𝒂 = where: K a = acid dissociation constant
[𝑯𝑿 ]

➢ The magnitude of K a indicates the tendency of the hydrogen atom to ionize


➢ The larger the value of K a, the stronger is the acid.
Weak Acids

Examples of Weak acids in water with their Ka values at 25oC


Weak Acids Ka
Hydrofluoric acid 6.8 x 10 -4
Nitrous acid (HNO 2) 4.5 x 10 -4
Benzoic acid 6.3 x 10 -5
(HC7H5OO/CH7H5O2)
Acetic acid (CH 3COOH) 1.8 x 10 -5
Hypochlorous acid (HClO) 3.0 x 10 -8
Hydrocyanic acid (HCN) 4.9 x 10 -10
Phenol (HC 5O) 1.3 x 10 -10
Exercise:
In a 0.25 M solution of benzyl amine, C7H7NH2, the concentration of OH -(aq) is 2.4 x 10 -3 M. What is the %
ionization and the value of K b for the aqueous ionization of benzyl amine?
pH AND BUFFERS
Aqueous Ionic Systems
❖The unique formations of lime stone
caves
❖Vast expanses of oceanic coral reefs
❖ Why do some lakes become acidic
when showered with acid rain while
others remain unaffected?
❖ How does blood maintain a constant
pH in contact with countless acid-base
reactions?
What is Buffer and How it works?
❑A buffer is something that lessens the impact
of an external force
❑ An acid-base buffer is a solution that lessens
the impact on pH from the addition of acid-
base.
❑ A buffer must have an acidic component that
reacts with the added OH- and a basic
component that reacts with the added H3O+,
but these components can’t be acid-base
because they would neutralize each other
❑ Most often, the components of a buffer are
a conjugate acid-base pair (weak acid and
conjugate base or weak base and a conjugate
acid)
Presence of Common Ion
❑ Buffer works through the common-ion effect

Buffer after addition of H3O+ Buffer with equal Buffer after addition of OH-
concentrations of conjugate
base and acid

H2O + CH3COOH H3O+ + CH3COO- CH3COOH + OH- H2O + CH3COO-


Presence of Common Ion
Buffer with equal Buffer after addition of OH-
Buffer after addition of H3O+ concentrations of conjugate
base and acid

H2O + CH3COOH H3O+ + CH3COO- CH3COOH + OH- H2O + CH3COO-

❑ Note: The common ion effect occurs when a given ion is added to an equilibrium mixture that
already contains that ion, and the position of the equilibrium shifts away from forming it
Relative Concentrations of Buffer
Components
❑ A buffer works because large components of the acidic [HA] and basic [A]
components consume small amounts of OH- and H3O+ respectively.

❑ Consider what happens to a solution with high concentration of [CH3COOH] and [CH3COO-],
when small amount of acid and base is being added.
[𝐂𝐇𝟑 𝐂𝐎𝐎− ] [𝐇𝟑 𝐎+ ]
𝐊𝐚 =
[𝐂𝐇𝟑 𝐂𝐎𝐎𝐇]
Solving for [H3O+] gives,
[𝐂𝐇𝟑 𝐂𝐎𝐎𝐇]
[𝐇𝟑 𝐎+ ] = 𝐊 𝐚 x
[𝐂𝐇𝟑 𝐂𝐎𝐎− ]

[𝐂𝐇𝟑 𝐂𝐎𝐎𝐇]
Thus, the concentration ratio is:
[𝐂𝐇𝟑 𝐂𝐎𝐎− ]
➢ If the ratio [HA]/[A-] goes up, [H3O+] goes up
➢ If the ratio [HA]/[A-] goes down [H3O+] goes down
Relative Concentrations of Buffer
Components
Buffer with equal Buffer after addition of OH-
Buffer after addition of H3O+ concentrations of conjugate
base and acid

H2O + CH3COOH H3O+ + CH3COO- CH3COOH + OH- H2O + CH3COO-

❑ Note that: the conversion of one component into the other produces a small change in the buffer-
component concentration and consequently a small change in [H3O+] and in pH.
The Henderson-Hasselbach Equation
HA + H2O H3O+ + A-
[H3O+] [A-]
Ka =
[HA]
Ka [HA]
[H3 O+] =
[A-]
[A-]
- log[H3O+] = - log Ka + log
[HA]

[base]
pH = pKa + log
[acid]
The Henderson-Hasselbach
Equation
[base]
pH = pKa + log
[acid]

❑This relationship allows us to solve directly for pH instead of having to calculate the H3O+
concentration first
Buffer Capacity
❑ Buffer capacity is a measure of the “strength” of the buffer, its ability to maintain the pH
following the addition of strong acid or base. Capacity ultimately depends on the concentration,
both absolute and relative concentration.

❑ Absolute concentration- the more concentrated the buffer components, the greater the buffer
capacity. Thus for the given amount of added [H3O+] and [OH-], the pH of a higher capacity buffer
changes less than the pH of a lower capacity buffer.
❑Note that buffer pH is independent of buffer capacity. A buffer made of equal volumes of 1.0 M
CH3COOH and 1.0 M CH3COO- has the same pH as buffer made of equal volumes of 0.10 M
CH3COOH and 0.10 CH3COO-, but the more concentrated buffer has the greater buffer capacity.

❑ Relative concentration- the closer the component concentration to each other the greater the
buffer capacity. The less the concentration ratio changes, the less the pH change. A buffer has the
highest capacity when the component concentrations are equal. When the ratio = 1 then pH=pKa
Buffer Range
❑Buffer range is the pH range over which the buffer is effective and is also related to
the relative buffer-component concentrations. The further the concentration ratio is
from 1, the less effective the buffer (the lower the buffer capacity). Buffers has a
usable range within ±𝟏 pH unit of the pKa of the acid component:

10 1
pH = pKa + log = 𝑝𝐾𝑎 + 1 pH = pKa + log = 𝑝𝐾𝑎 − 1
1 10
Buffer Capacity and Buffer Range
Buffer
Importance of Buffer in Drug
Absorption
[Drug-]
pH = pKa + log
[Drug-H]

Acidic drug:

Basic drug:

A drug passes through membranes more readily if it is uncharged.


Importance of Buffer in Drug
Absorption
[Drug-]
pH = pKa + log
[Drug-H]

Example: For a weak acid, such as aspirin, the uncharged


HA can permeate through membranes , but A– cannot.
For a weak base, such as morphine, the uncharged form,
B, penetrates through the cell membrane, but BH+ does
not.

• The effective concentration of the permeable form of


each drug at its absorption site is determined by the
relative concentrations of the charged (impermeant)
and uncharged (permeant) forms
Importance of Buffer in Drug
Absorption
Example: For a weak acid, such as
aspirin, the uncharged HA can permeate
through membranes , but A– cannot. For
a weak base, such as morphine, the
uncharged form, B, penetrates through
the cell membrane, but BH+ does not.
aspirin

[Drug-]
pH = pKa + log
[Drug-H]

morphine
How to Prepare a Buffer
1. Choose the conjugate acid-base pair.

2. Calculate the ratio of buffer component concentrations.

3. Determine the buffer concentration.

4. Mix the solution and adjust the pH.


Biological Buffers
You need to produce a buffer solution that has a pH of 5.270. You already have a solution that
contains 10.0 mmol of acetic acid. How many millimoles of sodium acetate will you need to add
to this solution. The pKa of acetic acid is 4.752

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