7/25/2013

Acids and Bases: Chem 16

+
H (aq)
+ OH -(aq)

Arrhenius Definition

Acids and Bases: Chem 16

H 2 O (l )

ACIDS donates H+

BASES donates OH-

HNO3, H3PO4, H2SO4, HCl, HI, HBr,

CH3COOH, organic-COOH, H2SO3

NaOH, KOH, LiOH, CsOH,

Mg(OH)2,Sr(OH)2,Ba(OH)2 , Ca(OH)2

Bronsted-Lowry Definition

Bronsted-Lowry H O + NH OH- + NH +
2 (l)
3(g)
(aq)
4(aq)
Definition

ACIDS donates H+
(proton donor)

BASES accepts H+
(proton acceptor)

HNO3, H3PO4, H2SO4, HCl, HI, HBr,

CH3COOH, organic-COOH, H2SO3

NH3, organic-NH2, NaOH, KOH, LiOH,

CsOH, Mg(OH)2,Sr(OH)2,Ba(OH)2 , Ca(OH)2

Acids and Bases: Chem 16

Acids and Bases: Chem 16

Amphoterism:

Lewis Definition

Species that can behave as an acid or base are called

amphoteric.

NH
base

+ H 2O
NH

NaF + BF 3

Zn(OH)2 + 2 OH - Zn(OH)24-

acid

HPO43- + H2O
H2PO42- + OHHPO43- + H2O
PO43- + H3O+

+ OH

acid

Zn(OH)2 + 2 HNO3 Zn(NO3 ) 2 + 2 H 2 O

Proton transfer reactions in which a species behaves
as either an acid or base is called amphiprotic

+
4

Na

+ BF

base

ACIDS electron-pair acceptor

H+ ( all molecules with H+)

Electron deficient molecules (below-octet
atoms eg. Boron cmpds)

BASES electron-pair donor

OH- ( all molecules with OH-)
Molecules with lone e- pairs

7/25/2013

Acids and Bases: Chem 16
17

Acids and Bases: Chem 16
17

The Autoionization of water
+
H 2 O (l) + H 2 O (l)
H 3 O (aq)
+ OH-(aq)

Kc =

Equilibrium-constant expression:

But concentration of water is constant

(and large) at 25oC, therefore:

[ H 3O + ][OH - ]
[H 2 O]2

K c K w = [H 3O + ][OH - ]
K w = (1.00x 10-7 )(1.00x 10-7 )

Experimental concentration H+ is
determined to be 1.00x10-7 at 25oC,
therefore:

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

pOH = -log[OH-]
Kw = 1.00 x 10-14 = [H+][OH-] at 25oC
pOH + pH = 14.00

Proof:
-log Kw = -log [1.00 x 10-14] = -log ([H+][OH-])
-log Kw = 14.00 = -log[H+] + -log[OH]14.00 = pH + pOH

K w = 1.00x 10-14 at 25o C

Acids and Bases: Chem 16
17

What is pH of water at its normal boiling point? Is

it acidic or basic?
Given:
HfoH2O(l) = -285.83 kJ/mol
Hfo OH-(aq) = -230.0 kJ/mol

Calculate the [H3O+], pH, [OH-], and pOH for a 0.020 M HNO3
solution.
Is HNO3 a weak or strong acid?
What is the [H3O+] ?
100%
HNO 3 + H 2 O
H 3 O + + NO 3-

0.020M

[H O ] = 2.0 10
pH = -log(2.0 10
+

0.020M 0.020M

When concentration of acid reaches 1.00 x 10-5 and below,

the [H+] of H2O should be added, where [H+] = 1.00 x 10-7
(only used at 25oC)

Example: What is the pH of a solution prepared by diluting

1.0 mL of 0.1 M HCl with 1000 liters of water?

pH = 1.70

7/25/2013

Acids and Bases

Relative Strengths of Acids and Bases
Conjugate Acid-Base Pairs

The weaker the acid or base, the stronger the conjugate partner.

The stronger the acid or base, the weaker the conjugate partner.

NaCH3OO(aq) + HCl(aq)
NaCl(aq) + CH3COOH(aq)
Na 2CO3(aq) + 2CH3OOH(aq)
2NaCH3OO(aq) + H 2CO3(aq) H 2O(l) + CO2(g)

Ionization Constants for Monoprotic

Weak Acids and Bases
Consider an aqueous solution of acetic acid,
CH3COOH. What is the equilibrium constant
expression?
CH3COOH(aq) + H2O(l) CH3COO-(aq) + H3O+(aq)

Kc =

[H 3O + ][CH3COO - ]
[CH 3COOH][H2O]

But [H2O] = 55.6 M, very high and almost constant, therefore

STRONGER
ACID and BASE

Kc Ka =

WEAKER
ACID and BASE

[ H 3 O + ][CH 3 COO - ]
[CH 3 COOH]

Because of its simplified form, we can write

the equation for dissociation as
CH3COOH(aq) CH3COO-(aq) + H+(aq)

[H + ][CH 3COO- ]
Ka =
[CH 3COOH]

Kc Ka =

[H 3 O + ][CH 3 COO - ]
[CH 3 COOH]

For weak bases,

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

[OH ][NH 4 ]
Kb =
[NH3 ]

[OH ][NH 4 ]
Kc =
[NH3 ][H 2O]

Kb is the base-dissociation constant.

Does the base really dissociate, like acids?

HA H+ + A-

Ka =

[H + ][conjugate base]
[acid]

B- + H2O OH- + BH

Kb =

[OH ][conjugate acid]

[base]

Ka is the acid-dissociation constant

7/25/2013

Ionization Constants for Monoprotic Weak Acids

and Bases

The ionization constant values for several acids are given below.
Which acid is the strongest?

Calculate the concentrations of the various species in

0.15 M acetic acid, CH3COOH, solution.

Acid

Formula

Ka value

Acetic

CH3COOH

1.8 x 10-5

Nitrous

HNO2

4.5 x 10-4

Hydrofluoric

HF

7.2 x 10-4

Hypochlorous

HClO

3.5 x 10-8

Hydrocyanic

HCN

4.0 x 10-10

ALWAYS write down the ionization reaction and

the ionization constant expression.

CH 3COOH + H 2 O
H 3O + + CH 3COO -

[H O ][CH COO ] = 1.8 10

=
+

Ka

[CH 3COOH ]

The order of increasing acid strength for these weak

acids is:

HF > HNO 2 > CH 3COOH > HClO > HCN

H 3 O + + CH 3 COO CH 3 COOH + H 2 O
Initial [ ]
Change

0.15M
- xM

Equilibrium [ ] ( 0.15-x)M

+ xM

+ xM

+ xM

+ xM

Short-cut: Use the simplfying assumption-

Since x << 0.15, assume that 0.15 x 0.15

If Ka /[ ]initial is < 1.0x10-3 , the simplifying assumption is valid

7/25/2013

Percent Ionization of Weak

Acids/Bases

Calculate the percent ionization of 0.15 M

hydrocyanic acid, HCN. Ka = 4.0 x 10-10
Compare the %ionization of HCN and HOAc.

Calculate the percent ionization of 0.15 M acetic acid. The

percent ionization of acetic acid is

[CH COO ]
% ionization =
-

equil

[ ]

or H +

[CH3COOH]original

% ionization =

equil

100%

1.6 10 3 M
100% = 1.1%
0.15M

Solution
0.15 M
HOAc

Ka
1.8 x 10-5

[H+]
1.6 x 10-3

pH
2.80

% ionization
1.1

0.15 M
HCN

4.0 x 10-10

7.7 x 10-6

5.11

0.0051

Solvolysis: Reaction of Acid/Base with solvent

Solvolysis is the reaction of a substance with the solvent
in which it is dissolved.
Hydrolysis refers to the reaction of a substance with water
or its ions.

Consider the acid HA

HA + H2O A- + H3O+
Ka
Reverse form:
A- + H3O+ HA + H2O
Ka = 1/Ka
Consider the conjugate base, AA- + H2O HA + OHKb
Reverse form:
Kb = 1/Kb
HA + OH- A- + H2O

Note that the [H+] (or %ionization) in 0.15 M acetic

acid is 215 times greater than for 0.15 M HCN.

Solvolysis: Reaction of Acid/Base with

solvent
How is Ka related to Kb?
HA + H2O A- + H3O+
Ka
A + H2O HA + OH
Kb
H2O + H2O H3O+ + OH-

K w = Ka x K b

Kb =

Kw

Kw
Ka

Ka =

Kw
Kb

7/25/2013

The order of increasing acid strength for the weak

acids is:

Strengths of Acids and Bases

HF > HNO 2 > CH3COOH > HClO > HCN

7.2 x

10-4

4.5 x

10-4

1.8 x

10-5

3.5 x

10-8

4.0 x

10-10

The order of increasing base strength of the anions

(conjugate bases) of the same acids is:

F- < NO -2 < CH 3COO - < ClO - < CN 2.2 x 10-11 1.4 x 10-11

5.6 x 10-10

The stronger the acid/base, the weaker is its conjugate

2.9 x 10-7

Kb =

2.5 x 10-5

Kw
Ka

Strengths of Acids and Bases

Down a group: size, energy to break H- bond
(
electronegativity), acidity

Strengths of BINARY Acids - acid strength increases with

decreasing H-X bond strength.
VIIA hydrohalic acids

Bond strength has this periodic trend

HF >> HCl > HBr > HI
Acid strength has the reverse trend.
HF << HCl < HBr < HI
VIA hydrides.

Bond strength has this trend.

H2O >> H2S > H2Se > H2Te
The acid strength is the reverse trend.
H2O << H2S < H2Se < H2Te

Strengths of Acids and Bases

TERNARY ACIDS - hydroxides of nonmetals
that produce H3O+ in water.
Consist of H, O, and a nonmetal.

Arrange in order of increasing acidity:

NH3, OH2, HF

NH3 < OH2 < HF
(Electronegativity trend:
NH3 < OH2 < HF)

HClO4

H3PO4

Across a period: electronegativity, acidity

7/25/2013

Strengths of Acids and Bases

Strengths of Acids and Bases

Acidity of ternary acids with same central

element increase with increasing oxidation state
of central element, and increasing O atoms
HClO < HClO2 < HClO3 < HClO4
weakest
strongest

for phosphorus
ternary acids of the sameHowever
group and
same
ternary
acids:
number of O atoms increase in acidity with
3PO
2 > H3POatom
3 > H3PO4
increase electronegativityHof
central
relative position of H is
H2SeO4 < H2SO4 important (based on
HBrO4 < HClO4 structures)
HBrO3 < HClO3

+1

Cl oxidation states
+3
+5
+7

Hard and Soft Acids and Bases

From previous discussion, the STRENGTH of an
acid or a base depends on the value of its
dissociation constant Ka or Kb, respectively
Hardness or Softness of an acid/base depends
on POLARIZABILITY of molecule
Recall that Polarizability is used in describing the
type of IMFA of molecules
The concept of Hardness or Softness of acids/bases
is Lewis-structure dependent, therefore it is a
concept applied only in the LEWIS DEFINITION of
acids/bases.

More polarizable molecules (greater # of eor lone pairs) SOFT Lewis

acids/bases
Less polarizable molecules HARD Lewis
acids/bases
In general, molecules that involve

HARD acid-HARD base

SOFT acid-SOFT base

>

HARD acid-SOFT base

SOFT acid-HARD base

Dissociation
constant

7/25/2013

Hard Lewis acid

In a 0.12 M solution of a weak monoprotic acid, HY, the acid is

5.0% ionized. Calculate the dissociation constant for the weak
acid.
Which is the Hardest Lewis base? Which is the softest?

F-

NO -2

CH 3 COO -

ClO -

CN SOFTEST
Lewis base

HARDEST
Lewis base

The pH of a 0.10 M solution of a weak monoprotic acid, HA,

is found to be 2.97. What is the value of its dissociation
constant?

Polyprotic Acids/Bases
Many weak acids contain two or more acidic hydrogens.
Examples include H3PO4 and H3AsO4.
The calculation of equilibria for polyprotic acids is done in a
stepwise fashion.
There is a dissociation constant for each step
Consider arsenic acid, H3AsO4, which has three ionization
constants.
1 Ka1 = 2.5 x 10-4
2 Ka2 = 5.6 x 10-8
3 Ka3 = 3.0 x 10-13

Calculate the concentration of all species in 0.100 M

arsenic acid, H3AsO4, solution.
You may apply the simplifying assumption in each step (1 ICE table/
dissociation)

7/25/2013

+
H 2 CO3(aq) + H 2 O (l) HCO3(aq)
+ H 3 O (aq)
2+
HCO-3(aq) + H 2 O (l) CO3(aq)
+ H 3 O (aq)
23(aq)

CO

+ H 2 O(l) HCO

3(aq)

(aq)

+ HO

HCO-3(aq) + H 2 O(l) H 2 CO3(aq) + HO(aq)

K a1

K a1 = 4.4 x 10 -7
K a2 = 4.7 x 10 -11
K b1 = 2.1 x 10

-4

K b2 = 2.3 x 10-8

Ka1 = 7.50 x 10-3

+
H2PO-4(aq) + H2O(l) HPO24(aq)
+ H3O(aq)

Ka2 = 6.20 x 10-8

+
HPO24(aq)
+ H2O(l) PO34(aq)
+ H3O(aq)

Ka3 = 3.60 x 10-13

PO 34(aq)
+ H 2 O (l) HPO 24(aq)
+ HO (aq)

K b1

HPO 24(aq)
+ H 2 O (l) H 2 PO -4(aq) + HO (aq)

K b2

H 2 PO -4(aq) + H 2 O (l) H 3 PO 4(aq) + HO (aq)

K b1
Kw

K a2

+
H3PO4(aq) + H2O(l) H2 PO-4(aq) + H3O(aq)

K a1
K a2

K b2

K a3

The behaviour of an amphiprotic species (acting

as base or acid) depends on its dissociation
constants

HCO-3(aq) + H 2 O(l) H 2 CO3(aq) + OH(aq)

2HCO-3(aq) + H 2 O(l) CO3(aq)
+ H3O+(aq)

K b2 = 2.38 x 10-8

Kw

K b3

K b1
K b2
K b3

What is the pH of the resulting solution obtained

by dissolving 1.52 g of NaH2PO42H2O in 50.00
mL water? If the salt added was Na2HPO42H2O
instead, will the solution be basic or acidic?

K a2 = 4.80 x 10-11

+
H 2 PO-4(aq) + H 2 O(l) HPO24(aq)
+ H3O(aq)

K a2 = 6.20 x 10-8

H 2 PO-4(aq) + H 2 O(l) H3 PO4(aq) + OH(aq)

K b3 = 1.33 x 10-12

+
HPO24(aq)
+ H 2 O(l) PO34(aq)
+ H 3O(aq)

K a3 = 3.6 x 10-13

HPO24(aq)
+ H 2 O(l) H 2 PO-4(aq) + OH(aq)

K b2 = 1.61 x 10-7

You accidentally spilled muratic acid (2.0 M HCl)

on the rubber slippers of your room mate. To
neutralize the acid, you looked for a base in your
dorm stock room, and you found two salts
sodium bicarbonate and sodium phosphate.
Which of the two salts will you use?

7/25/2013

Inorganic Lewis Acids Hydrolysis of

Metal Ions
Because metal ions are positively charged, they
attract the electrons of oxygen atoms in water.
Depending on the strength of electron interacting
with the cation, the water molecule can turn into
hydroxide anion and release H+
Fe(H2 O) 63+( aq)

2+
+
Fe(H2 O)5 (OH)(aq)
+ H (aq)

K a = 2.0 x 10-3

Salts of acids and bases

Aqueous solutions of salts of strong acids and strong bases
are neutral
Examples: NaCl (from HCl and NaOH)
K2SO4 (from KOH and H2SO4)

Aqueous solutions of salts of strong bases and weak acids

are basic
Examples: NaCN (from NaOH and HCN)
K2C2O4 (from KOH and H2C2O4)

Aqueous solutions of salts of weak bases and strong acids

are acidic
Examples: NH4Cl (from NH3 and HCl)
(CH3)3NHBr ((CH3)N and HBr)

The acid strength of these ion-complexes acting as

Lewis acids depend on size and charge of cation
center
Na(NO3)
7.0

Ca(NO3)2
6.9

Zn(NO3)2
5.5

Al(NO3)3
3.5

How about KHC2O4? NaHSO4? LiHSO3?

Salts of acids and bases

Aqueous solutions of salts of weak bases and weak
acids can be neutral, basic or acidic.
The values of Ka and Kb determine the pH.
NH4CH3COO?
Compare Ka of NH4+ vs Kb of OAcMgNH4PO4?
Compare Ka of NH4+ and Mg2+ vs Kb of OAcNH4(HCO3)?
Compare Ka of NH4+ vs Kb/Ka of amphiprotic HCO3-

Common Ion Effect

and
Buffers/Buffer Capacity

10

7/25/2013

Common Ion Effect

A special name for a Le Chatelier-based shift
Consider a solution of 0.05 M acetic acid, CH3COOH (50.00
mL)

CH3COOH(aq) + H 2 O(l )

+
CH3COO(aq)
+ H 3O(aq)

K a = 1.8 x 10-5

Common Ion Effect

A special name for a Le Chatelier-based shift

Consider a solution of 0.05 M acetic acid,

CH3COOH (50.00 mL)

Describe the direction of equilibrium shift

Describe the pH of the final mixture

After adding 10.00 mL of 0.5 M HCl

(aq)

CH3COOH(aq) + H 2 O( l)
CH3COO

+ H3O

+
(aq)

After adding 10.00 mL of 0.5 M HCl

DECREASE pH, more ACIDIC

After adding 10.00 mL of 0.5 M NaCH3COO

+
CH3 COOH(aq) + H 2 O ( l )
CH3 COO(aq)
+ H 3O (aq)

After adding 10.00 mL of 0.5 M NaCH3COO

INCREASE pH, less ACIDIC

In COMMON-ION effect, the direction of shift of equilibrium is always towards the

side that diminishes the added common/similar ion

Buffers
Solutions that contain BOTH acid component and
its conjugate base

Henderson-Hasselbalch Equation
Simplified equation for pH calculation involving
buffers

Conjugate base is directly added, not the one

calculated from equilibrium
Examples :
Acetic acid added with sodium acetate
Ammonium chloride added with aqueous ammonia solution

Solutions that resist drastic pH changes

11

7/25/2013

Buffers

Common Ion Effect Buffers

What is pH of a buffer that is 0.12 M in lactic acid, HC3H5O5,

and 0.10 M in sodium lactate?
Ka = 1.40 x 10-4
C 4 H 4 O 3 COOH

(aq)

+ H 2O (l)

C 4 H 4 O 3 COO

0.12 M

+ H 3 O +(aq)

+x

0.12 - x

+x

0.10 + x

(x)(0.10 + x)
(0.12 x)

pH = pK a +

(0.10)
(0.12)

Non-buffer Case - Consider the a solution of 50.00 mL of 0.05 M acetic

acid, CH3COOH. Calculate the pH of the final mixture after adding 10.00
mL of 0.05 M HCl.
 Because HCl is a strong acid, it directly contributes to the initial concentration of
H3O+ in the equilibrium calculation
 Set-up ICE table in MOLE basis, then convert to molarity when
calculating/equating to Ka.

0.10 M

-x

Ka =

(aq)

CH 3 COOH

(50.00 mL)
(0.05 M)

-x

(aq)

+ H 2O (l)

CH 3 COO

(aq)

+
+ H 3 O (aq)

(10.00 mL)
(0.05 M)

+x

+x

The most important aspect of buffer solutions is that they resist drastic
changes of pH upon adding strong acids or bases!

Common Ion Effect Buffers

Buffer CASE - Consider a solution of 50.00 mL 0.05 M acetic acid

(CH3COOH) and 0.05 M sodium acetate (NaCH3COO). Calculate the pH of
the final mixture after adding 10.00 mL of 0.05 M HCl.

Henderson-Hasselbalch Equation

Step 1: STOICHIOMETRIC calculation

HA + H2O A- + H3O+

B + H2O BH+ + HO-

 HH equation only used when salt is present that is, present separately, not the
[salt] from ICE calculation
Step 2: EQUILIBRIUM calculation, HH

( 40 .00 mL)(0.05 M)

( total volume = 60.00 mL)

pH = pK a + log
(60.00 mL)(0.05 M)

(total volume = 60.00 mL)

Which has the lowest change in pH (pH)?

 The salt-component must be added separately, or generated by neutralizing the

main component
 In calculations involving buffers, ICE table must be in terms of MOLES especially if
volumes are not same. However, equating with Ka must be in MOLARITY.
 HH equation is allowed only when simplifying assumptions are valid

 Try calculating the pH after adding 10.00 mL of 0.05 M NaOH (instead HCl) for the 2 cases.

12

7/25/2013

Preparation of Buffers
Buffers can be prepared in three ways
Adding a solid component to a liquid component
Ex. NaCH3COO solid added to a solution of acetic acid (acetic-acetate
buffer)

Neutralizing a liquid component with a strong opposite

component
Ex. Aqueous ammonia added with liquid HCl (ammonia-ammonium
buffer)
Aqueous phosphoric acid added with solid NaOH (phosphate
buffer)

Mixing two solid components in the same volume of water

Preparation of Buffers
How many grams of NH4Cl must be added to 2.0 L
of 0.10 M NH3 to form a buffer of pH 9.00?
Kb NH3 = 1.8 x 10-5
What volume of 0.5 M NaOH must be added to 50 mL
of 0.1 M benzoic acid (C6H5COOH) to make 100.0 mL of
0.05 M benzoate buffer that is pH 4.5?
Ka benzoic acid = 6.3 x 10-5

Ex. Solid NaH2PO4H2O and solid Na2HPO47H2O dissolved in water

(phosphate buffer)

Preparation of Buffers

Prepare a 100.0 mL 0.1 M phosphate buffer, pH 8.00.

Given:
H3PO4
pKa1 = 2.12
pKa2 = 7.21
pKa3 = 12.38

Molarity H3PO4 (liquid) = 14.85 M

Formula weight
NaH2PO4H2O = 137.99 g/mole
Na2HPO47H2O = 268.07 g/mole

+
H 2 PO -4(aq) + H 2 O (l) HPO 24(aq)
+ H 3O (aq)

pH = pK a2 + log

pK a2 = 7.21

(moles HPO 24 - )
(moles H 2 PO -4 )

moles H 2 PO -4 + moles HPO 24 - = total moles buffer components

moles H 2 PO -4 + moles HPO 24 - =

(100.0 mL)
(0.1 M)
(1000 mL )
1L

Buffer Capacity
Amount of acid or base (usually in mL) needed to
change the pH of a buffer solution by 1 degree.
Compare the two buffers:
- 100 mL of 1.0 M NaCH3COO and 1.0 M CH3COOH
- 100 mL of 0.1 M NaCH3COO and 0.1 M CH3COOH
- Which has the highest buffer capacity relative to 1.0
M NaOH?

13

7/25/2013

Acid-Base Indicators

Acid-Base Neutralizations:
Indicators, Titrations
and
pH curves

The point at which chemically equivalent amounts of acid and

base have reacted is called the equivalence point.
The point at which a chemical indicator changes color is called
the end point.
HIn (aq) + H 2O ( l )
color 1
In (aq) + H 2 O ( l )

+
In (aq) + H 3O (aq)

color 2

color a

Acidic indicator

HIn (aq)
+ OH (aq)

Basic indicator

color b

Acid-Base Indicators

Acid-Base Indicators

The equilibrium constant expression for an indicator

would be expressed as:

Color change ranges of some acid-base indicators

Ka =

[H3O+ ][In- ]
[HIn]

Ka
[In- ]
=
[H3O+ ] [HIn]

pH range when indicator

changes its color depends
largely on Ka of the indicator

Indicator
Methyl violet
Methyl orange
Litmus
Phenolphthalein

Color in
Color in
acidic
pH range basic range
range
Yellow
0-2
Purple
Pink
3.1 4.4
Yellow
Red
4.7 8.2
Blue
Colorless 8.3 10.0
Red

14

7/25/2013

Titration Curves

Strong Acid/ Strong Base Titration Curve

Strong Acid titrated with Strong Base

SA-SB curve
14

Given: 25.00 mL of 0.5 M HClO4, calculate the pH of the resulting

solution after adding the following volumes of 0.5 M NaOH:

13
12
11
10

Phenolphthalein

Mmoles
NaOH

Mmoles
HClO4
remaining

Total
Volume
(mL)

[H+]final

pH

0.00

0.0

12.5

25.0

0.5000

0.301

5.00

2.5

10.0

30.0

0.3333

0.477

10.00

5.0

7.5

35.0

0.2143

0.669

15.00

7.5

5.0

40.0

0.1250

0.903

Volume of
0.5 M NaOH
(mL)

8
pH 7

Litmus

Methyl orange

3
2

Methyl violet

1
0

20.00

10.0

2.5

45.0

0.0555

1.256

25.00

12.5

50.0

1x10-7

7.000

30.00

15.0

55.0

2.2x10-13

12.657

10

Titration Curves

15
20
25
Volume Titrant (0.5 M NaOH)

30

35

40

WA-SB curve

Weak Acid titrated with Strong Base

14

Given: 25.00 mL of 0.5 M CH3COOH, calculate the pH of the resulting

solution after adding the following volumes of 0.5 M NaOH:

13
12
11
10

Volume of
0.5 M
NaOH (mL)

Mmoles
NaOH

Mmoles
CH3COOH
remaining

Mmoles
CH3 COOproduced

Total
Volume
(mL)

pH

0.00

0.0

12.5

25.0

0.301

5.00

2.5

10.0

2.5

30.0

4.143

10.00

5.0

7.5

5.0

35.0

4.569

Phenolphthalein

9
8
pH

Litmus

15.00

7.5

5.0

7.5

40.0

4.921

20.00

10.0

2.5

10.0

45.0

5.348

Methyl orange

3
2

Methyl violet

25.00

12.5

12.5

50.0

9.071

30.00

15.0

12.5

55.0

12.658

0
0

10

15

20

25

30

35

40

Titrant volume

15

7/25/2013

WA vs SB Titration Curve Regions

WA-SB curve
14

lactic curve

11

HClO curve

10

12

Buffer Region: HH Equation

pH = pKa + log [moles titrant/(moles analyte
moles titrant )]

11
10

Equivalence Region: Use ICE

and Kb
pOH =
(pKb + p[moles HA/total
volume])

At half equivalence point:

pH = pKa

7
6

Phenolphthalein

pH

acetic curve

12

Buffer Region: HH Equation

pH = pKa + log (moles A- /moles HA)

13

14
13

Excess base region:

pOH = -log (moles excess base/ total volume)

8
7

Litmus

6
5

Methyl orange

Initial Region: Use ICE

and Ka
pH = (pKa + pCHA)

3
2

0
0

10

15

20

25

30

35

40

Methyl violet
0

10

15

20

25

30

35

40

Titrant volume

Titration
Curve of
Different
Acids vs
Strong Base

A 0.1044-g sample of an unknown monoprotic acid required

22.10 mL of 0.0500 M NaOH to reach the endpoint. (a) What
is the molecular weight of the acid? (b) As the acid is titrated,
the pH of the solution after the addition of 11.05 mL of the
base is 4.89. What is the Ka of the acid?

A biochemist needs 750 mL of an acetic acid-sodium acetate

buffer with pH 4.50. Solid sodium acetate, NaC2H3O2, and
glacial acetic acid, HC2H3O2, are available. Glacial acetic acid is
99% pure by mass and has a density of 1.05 g/mL. If the
buffer is to be 0.20 M in HC2H3O2, how many grams of the salt
and how many milliliters of glacial acetic acid must be used?

16

7/25/2013

Weak H2A vs SB

Titration Curves of Polyprotic Acids vs SB

H2A + H2O HA- + H3O+
HA- + H2O A2- + H3O+

Excess base region:

pOH = -log (moles excess base/ total volume)
Equivalence Region: Use ICE and Kb1
pOH = (pKb1 + p[moles H2A/total volume])

Ka1
Ka2

Buffer Region: HH Equation

pH = pKa2 + log (moles A2- /moles HA-)

pH Curve will show:

 2 Equivalence points
 Buffer region similar to weak monoprotic acid region
 Amphiprotic region
First Equivalence Point: H2A + NaOH Na+ + HA- + H2O
Second Equivalence Point:

HA-

+ NaOH

Na+

A2-

+ H2O

Amphiprotic region starts at the 1st equivalence point region. The

region between the 1st equivalence point and 2nd equivalence point is
a buffer region composed of HA- and A2-. In this region, the buffer HAand A2- predominates the amphiprotic species HA-. 

Weak H3A vs Strong Base Titration

Buffer Region: HH Equation

pH = pKa1 + log (moles HA- /moles H2A)

Amphiprotic Region
pH = (pKa1 + pKa2)

Initial Region: Use ICE

pH = (pKa1+ pCH2A)

Suppose you want to do a physiological

experiment that requires a pH 6.5 buffer. You find
that the organism with which you are working is
stable to a certain acid and its sodium salts (H2X:
Ka1 = 2x10-2, Ka2 = 5.0x10-7). You have available
1.0 M of this acid and 1.0 M NaOH in the lab.
How much of the NaOH should be added to 1.0 L
of the acid to make a buffer at pH 6.50?

What is the pH of a solution made by mixing 0.30 mole

NaOH, 0.25 mole Na2HPO4 , and 0.20 mole H3PO4 with
water and diluting with 1.00 L?
H3PO4
pKa1 = 2.12
pKa2 = 7.21
pKa3 = 12.38

17