ACIDS and BASES

DEFINITIONS of Acids and Bases:

Arrhenius Theory
Acid: A molecular substance that ionizes in aqueous
solution to form hydrogen ions (H+).

Base: A substance that produces hydroxide ions (OH-)

in aqueous solution.
 Brønsted-Lowry Concept
An alternative definition:
Brønsted-Lowry Acid = Proton donor
Brønsted-Lowry Base = Proton acceptor

Works for non-aqueous solutions and explains why NH3 is basic:

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

Base: Acid:
H+ acceptor H+ donor
 Brønsted-Lowry Concept
Strong acids and bases almost completely ionize.
HNO3(aq) + H2O(l) H3O+(aq) + NO3-(aq)

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: Conj.Acid: Conj.Base:
H+ donor H+ acceptor H+ donor H+ acceptor

Conjugate acid-base pairs

 Acid Ionization Constants, Ka
When an acid ionizes in water:
HA(aq) + H22O(l) H33O++(aq) + A--(aq)

The acid ionization constant is used to report the degree

of ionization:

[A-][H3O+] (Water omitted, as usual)

Ka =
[HA]

Strong acids have large Ka values

Weak acid have small Ka values
 Dissociation Constants: Strong Acids
Conjugate Ka
Acid Formula
Base
 Perchloric   HClO4   ClO4-   Very large 
 Hydriodic   HI   I-   Very large 
 Hydrobromic   HBr   Br-   Very large 
 Hydrochloric   HCl   Cl-   Very large 
 Nitric   HNO3   NO3-   Very large 
 Sulfuric   H2SO4   HSO4-   Very large 
 Hydronium ion   H3O+   H2O   1.0 
 Dissociation Constants: Weak Acids
Conjugate Ka
Acid Formula
Base
 Iodic   HIO3   IO3-   1.7 x 10-1 
 Oxalic   H2C2O4   HC2O4-   5.9 x 10-2 
 Sulfurous   H2SO3   HSO3-   1.5 x 10-2 
 Phosphoric   H3PO4   H2PO4-   7.5 x 10-3 
 Citric   H3C6H5O7   H2C6H5O7-   7.1 x 10-4 
 Nitrous   HNO2   NO2-   4.6 x 10-4 
 Hydrofluoric  HF   F-   3.5 x 10-4 
 Formic   HCOOH   HCOO-   1.8 x 10-4 
 Benzoic   C6H5COOH   C6H5COO-   6.5 x 10-5 
 Acetic   CH3COOH   CH3COO-   1.8 x 10-5 
 Carbonic   H2CO3   HCO3-   4.3 x 10-7 
 Hypochlorous   HClO   ClO-   3.0 x 10-8 
 Hydrocyanic   HCN   CN-   4.9 x 10-10 
 Base Ionization Constants, Kb
For a base in water:

B:(aq) + H22O(l) BH++(aq) + OH--(aq)

The base ionization constant, Kb, is:

[BH+][OH-]
Kb = [B:]
If the base is an anion:
A-(aq) + H2O(l) HA(aq) + OH-(aq)
[HA][OH-]
Kb = [A ]
-
 Dissociation of Strong Bases
MOH(s)  M+(aq) + OH-(aq)

 Strong bases are metallic hydroxides (MOH)

Group I hydroxides (NaOH, KOH) are very
soluble
Group II hydroxides (Mg, Ca, Ba, Sr) are less
soluble
 Kb for Some Common Weak Bases
Many students struggle with identifying weak bases and
their conjugate acids.What patterns do you see that may
help you?
Conjugate Kb
Base Formula
Acid
Ammonia   NH3  NH4+  1.8 x 10-5 
 Methylamine  CH3NH2  CH3NH3+  4.38 x 10-4 
 Ethylamine  C2H5NH2  C2H5NH3+  5.6 x 10-4 
 Diethylamine  (C2H5)2NH  (C2H5)2NH2+  1.3 x 10-3 
 Triethylamine   (C2H5)3N   (C2H5)3NH+  4.0 x 10-4 
 Hydroxylamine  HONH2   HONH3+    1.1 x 10-8 
 Hydrazine H2NNH2  H2NNH3+    3.0 x 10-6 
 Aniline  C6H5NH2   C6H5NH3+    3.8 x 10-10 
 Pyridine  C5H5N   C5H5NH+    1.7 x 10-9 
 Relative Strength of Acids & Bases
Strong acids are better H+ donors than weak acids
Strong bases are better H+ acceptors than weak bases
• Stronger acids have weaker conjugate bases.
• Weaker acids have stronger conjugate bases.

HCl(aq) + H2O(ℓ) → H3O+(aq) + Cl-(aq)

strong
strongacid
acid very weak base
(100
(100%%ionized)
ionized) (no tendency to form
HCl)

HF(aq) + H2O(ℓ) H3O+(aq) + F-(aq)

weak
weakacid
acid F- readily forms
(many
(manyHF
HFare
areun-ionized)
un-ionized) HF
12
 Water can be Acid or Base
Water acts as a base when an acid dissolves in water:

HBr(aq) + H2O(l) H3O+(aq) + Br-(aq)

acid base acid base

But water also acts as an acid for some bases:

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

acid base acid base

Water is amphiprotic/amphoteric - it can donate or accept a

proton (act as acid or base).
 Autoionization of Water
Two water molecules can react to form ions.
Autoionization occurs:
Acid Base
H2O(l) + H2O(l) H3O+(aq) + OH-(aq)
Base Acid

Heavily reactant favored.

Only a very small fraction is ionized:
Kw = [ H3O+ ] [ OH- ] [H2O]2 is
ionization omitted…
constant for = (1.0 x 10-7)(1.0 x 10-7)
water = 1.0 x 10-14 (at 25°C)
 Ionization Constant for Water
Kw, like all equilibrium constants, is T-dependent.
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
 The pH Scale
pH is a means of expressing the acidity or basicity of a
solution.
 The pH scale
Acid concentration can vary over a very large range.
A logarithmic scale is more convenient:
pH = −log10[H3O+]

At 25°C a neutral aqueous solution has:

pH = −log10[1.0 x 10-7] = −(−7.00) = 7.00

Acidic solutions: pH < 7.00

Basic solutions: pH > 7.00
 The pOH scale
Base concentrations:
pOH = −log10[OH-]

A neutral solution (25°C) has:

pOH = −log10[1.0 x 10-7] = −(−7.00) = 7.00

Since Kw = [ H3O+ ][ OH- ] = 1.0 x 10-14

−log(KW)= −log[H3O+] + (−log[OH-]) = −log(1.0 x 10-14)

pKw = pH + pOH = 14.00

(Valid in all aqueous solns. at 25°C: acidic, neutral or basic)

pH of
common
solns:
A. Given two aqueous solutions (25°C).
Solution A: [OH-] = 4.3 x 10-4 M,
Solution B: [H3O+] = 7.5 x 10-9 M.
Which has the higher pH? Which is more acidic?

B. Calculate the hydronium and hydroxide ion

concentration of an aqueous solution with pH 4.21
 Measuring pH
H3O+ concentrations can be measured with an:
• Electronic pH meter:
 fast and accurate
 preferred method.

• Acid-base Indicator:
 substance that changes color within a narrow pH range
 may have multiple color change (e.g. bromthymol blue)
 one “color” may be colorless (e.g. phenolphthalein)
 cheap and convenient.
 Relationship between Ka and Kb values

For an acid-base conjugate pair: HA and A-

[H3O+][A-] [HA][OH-]
Ka x Kb = = [H3O+][OH] = Kw
[HA] [A-]

Phenol, C6H5OH, is a weak acid, Ka = 1.3 x 10-10 at 25°C.

Calculate Kb for the phenolate ion C6H5O-
 Reactions of Acids, Bases

Strong acid + strong base → salt solution, pH = 7

Strong acid + weak base → salt solution, pH < 7

Weak acid + strong base → salt solution, pH > 7

Weak acid + weak base → salt solution, pH = ?

Need K’s “strongest wins”
 The problem-solving approach
Make a habit of applying the following steps:

 Write the balanced equation and Ka expression.

 Define x as the unknown change in concentration that occurs during
the reaction. Frequently, x = [HA]dissoc, the concentration of HA that
dissociates, which, through the use of certain assumptions, also equals [H3O+]
and [A-] at equilibrium.
 Construct a reaction table (ICE) that incorporates the unknown.
 Make assumptions that simplify the calculations: usually that x is very
small relative to the initial concentration.
 Substitute the values into the Ka expression, and solve for x.
 Check that the assumptions are justified. (Apply the 5% rule) If they
are not justified, use the quadratic formula to find x.
A Weak Acid Equilibrium Problem
What is the pH of a 0.50 M solution of acetic
acid, HC2H3O2, Ka = 1.8 x 10-5 ?

Step #1: Write the dissociation equation

HC2H3O2  C2H3O2- + H+
A Weak Acid Equilibrium Problem
What is the pH of a 0.50 M solution of acetic
acid, HC2H3O2, Ka = 1.8 x 10-5 ?

Step #2: ICE it!

HC2H3O2  C2H3O2- + H+
I 0.50 0 0
C -x +x +x
E 0.50 - x x x
A Weak Acid Equilibrium Problem
What is the pH of a 0.50 M solution of acetic
acid, HC2H3O2, Ka = 1.8 x 10-5 ?

Step #3: Set up the law of mass action

HC2H3O2  C2H3O2- + H+
E 0.50 - x x x
2
5 ( x)( x) x
1.8 x 10  
(0.50  x) (0.50)
 A Weak Acid Equilibrium Problem
What is the pH of a 0.50 M solution of acetic
acid, HC2H3O2, Ka = 1.8 x 10-5 ?

Step #4: Solve for x, which is also [H+]

HC2H3O2  C2H3O2- + H+
E 0.50 - x x x

2
5 x
1.8 x 10  [H+] = 3.0 x 10-3 M
(0.50)
A Weak Acid Equilibrium Problem
What is the pH of a 0.50 M solution of acetic
acid, HC2H3O2, Ka = 1.8 x 10-5 ?

Step #5: Convert [H+] to pH

HC2H3O2  C2H3O2- + H+
E 0.50 - x x x

5
pH   log(3.0 x 10 )  4.52
A Weak Base Equilibrium Problem
What is the pH of a 0.50 M solution of ammonia,
NH3, Kb = 1.8 x 10-5 ?

Step #1: Write the equation for the reaction

NH3 + H2O  NH4+ + OH-

A Weak Base Equilibrium Problem
What is the pH of a 0.50 M solution of ammonia,
NH3, Kb = 1.8 x 10-5 ?

Step #2: ICE it!

NH3 + H2O  NH4+ + OH-

I 0.50 0 0
C -x +x +x
E 0.50 - x x x
 A Weak Base Equilibrium Problem
What is the pH of a 0.50 M solution of ammonia,
NH3, Kb = 1.8 x 10-5 ?

Step #3: Set up the law of mass action

NH3 + H2O  NH4+ + OH-

E 0.50 - x x x
2
( x)( x)
5 x
1.8 x 10  
(0.50  x) (0.50)
 A Weak Base Equilibrium Problem
What is the pH of a 0.50 M solution of ammonia,
NH3, Kb = 1.8 x 10-5 ?

Step #4: Solve for x, which is also [OH-]

NH3 + H2O  NH4+ + OH-

E 0.50 - x x x

2
5 x
1.8 x 10  [OH-] = 3.0 x 10-3 M
(0.50)
A Weak Base Equilibrium Problem
What is the pH of a 0.50 M solution of ammonia,
NH3, Kb = 1.8 x 10-5 ?

Step #5: Convert [OH-] to pH

NH3 + H2O  NH4+ + OH-

E 0.50 - x x x

5
pOH   log(3.0 x 10 )  4.52
pH 14.00  pOH  9.48
 Acid-base Titrations
In a titration, a solution of accurately known concentration
is added gradually added to another solution of unknown
concentration until the chemical reaction between the two
solutions is complete.
Equivalence point – the point at which the reaction is complete
Indicator – substance that changes color at (or near) the
equivalence point

Slowly add base

to unknown acid
UNTIL
the indicator
changes color
35
Chapter 4 Three Major Classes of Chemical Reactions

Be fo re Ne ar e nd At e nd
titratio n po int po int

A B C

H+ (aq ) + X– (aq ) + M+ (aq ) + OH– (aq ) H2 O(l ) + M+(aq ) + X– (aq )

F ig u r e 4 . 9 A n a c id -b a s e titra tio n .
A, In this procedure, a meas ured volume of the unknown
acid s olution is place d in a flas k beneath a buret containing the known (s tandard ized) bas e s olu-
tion. A fe w drops of indicator are added to the flas k; the indicator us ed here is phenolphthalein, 36
which is c olorle s s in ac id and pink in bas e. After an initial buret reading, bas e (OH ions ) is added
 Acid-base Titrations
 Primary standard – A chemical compound which can
be used to accurately determine the concentration of
another solution. Examples include KHP and sodium
carbonate.
 Standard solution – A solution whose concentration
has been determined using a primary standard.
 Standardization – The process in which the
concentration of a solution is determined by accurately
measuring the volume of the solution required to react
with a known amount of a primary standard.

37
Titrations can be used in the analysis of

Acid-base reactions

H2SO4 + 2NaOH 2H2O + Na2SO4

EXAMPLE:
A sodium hydroxide solution was standardized and used to
titrate 25.00 mL of a sulfuric acid solution. The titration requires
43.79 mL of the 0.1172 M NaOH solution to completely
neutralize the acid. What is the concentration of the H2SO4
solution?
38
 Think!
• Potassium hydrogen phthalate is a
very good primary standard.
– It is often given the acronym, KHP.
– KHP has a molar mass of 204.2
g/mol.

• In a titration experiment, a student finds that

23.48 mL of a NaOH solution are needed to
neutralize 0.5468 g of KHP. What is the
concentration (in molarity) of the NaOH solution?