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Acids and Bases II:

Review of Acid and Base Definition


Arrhenius Definition

+
(aq)

+ OH

(aq)

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
H 2O(l) + NH3(g) OH -(aq) + NH +4(aq)

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

Bronsted-Lowry Definition: Correct assignment of acid-base


conjugate pairs is based on properly drawn Lewis structures

Amphoterism:
Species that can behave as an acid or base are
called amphoteric.
Amphiprotic: special term for an amphoteric
species which involves proton transfer reactions
to show behavior as either an acid or base
HPO42- + H2O  H2PO4- + OHHPO42- + H2O  PO43- + H3O+

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

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

24

Lewis Definition
NH
base

+ H 2O
NH

+ OH

acid

NaF + BF 3
base

+
4

Na

+ BF

acid

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

Acids and Bases: Chem 16  17


The Autoionization of water

H 2O(l) + H 2O(l) H3O(aq) + OH(aq)

Equilibrium-constant expression:

But concentration of water is constant


(and large) at 25oC, therefore:

H+

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

[H 3O + ][OH- ]
Kc =
[H 2O]2
K c K w = [H 3O + ][OH- ]
K w = (1.00x 10-7 )(1.00x 10-7 )
K w = 1.00x 10-14 at 25o C

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

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
+

pH = 1.70

0.020M 0.020M

What is the 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


NOTE: When concentration of H+ coming from an acid source


(e.g. HA) 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?

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.

NaCH 3OO(aq) + HCl(aq)


NaCl(aq) + CH 3COOH (aq)
Na 2CO3(aq) + 2CH 3OOH (aq)
2NaCH 3OO(aq) + H 2CO3(aq) H 2O (l) + CO 2(g)

STRONGER
ACID and BASE

WEAKER
ACID and BASE

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)
[H 3O ][CH3COO ]
Kc =
[CH 3COOH][H 2O]

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

[H 3 O ][CH 3 COO ]
Kc Ka =
[CH 3 COOH]

[H 3 O ][CH 3 COO ]
Kc Ka =
[CH 3 COOH]

We can simply write the equation for


dissociation as
CH3COOH(aq) CH3COO-(aq) + H+(aq)
+
[H ][CH3COO ]
Ka =
[CH 3COOH]
Ka is the acid-dissociation constant

For weak bases,


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

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

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

Kb is the base-dissociation constant.


Does the base really dissociate, like acids?
+

HA

H+

A-

B- + H2O OH- + BH

[H ][conjugate base]
Ka =
[acid]
[OH ][conjugate acid]
Kb =
[base]

Ionization Constants for Monoprotic Weak Acids


and Bases


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

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

The order of decreasing acid strength for these weak


acids is:

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

Calculate the concentrations of the various species in


0.15 M acetic acid, CH3COOH, solution.


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]

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

0.15M

Change

- 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





1.0  10 , the simplifying assumption is valid

Percent Ionization of Weak


Acids/Bases


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

equil

100%

1.6 10 3 M
% ionization =
100% = 1.1%
0.15M

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.
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

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


Solvolysis - 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:
HA + OH- A- + H2O
Kb = 1/Kb

Solvolysis: Reaction of Acid/Base with solvent


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

Kw = Ka x Kb

Kw

Kw
Kb =
Ka

Kw
Ka =
Kb

The order of decreasing acid strength for the weak


acids is:

HF > HNO 2 > CH 3COOH > 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:
-

2.9 x 10-7

2.5 x 10-5

F < NO < 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

Kw
Kb =
Ka

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.

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?

Strengths of Acids and Bases


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

Strengths of Acids and Bases


Arrange in order of increasing acidity:
NH3, OH2, HF
 NH3 < OH2 < HF
(Electronegativity trend: NH3 < OH2 < HF)
Across a period: electronegativity, acidity

Strengths of Acids and Bases


TERNARY ACIDS - hydroxides of nonmetals
that produce H3O+ in water.
Consist of H, O, and a nonmetal.
HClO4

H3PO4

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
Cl oxidation states
+1
+3
+5

+7

Strengths of Acids and Bases


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

Base Strength of Amines

 The electronic properties of


the substituents (alkyl groups
enhance the basicity, aryl
groups diminish it).
 Steric hindrance offered by
the groups on nitrogen.

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)

+
H 2 CO 3(aq) + H 2 O (l) HCO3(aq)
+ H 3 O (aq)
2+
HCO3(aq)
+ H 2 O (l) CO 3(aq)
+ H 3 O (aq)
2
CO3(aq)
+ H 2 O(l) HCO3(aq)
+ HO(aq)

HCO3(aq)
+ H 2 O (l) H 2 CO3(aq) + HO(aq)

K a1

K b1
Kw

K a2

K b2

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

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

Ka1 = 7.50 x 10-3

+
H2 PO-4(aq) + H2O(l) HPO24(aq)
+ H3O(aq)

Ka2 = 6.20 x 10-8

24(aq)

HPO

+ H2O(l) PO

34(aq)

+
(aq)

+ H 3O

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 a1
K a2
K a3

Kw

K b1
K b2
K b3

K b3

The behaviour of an amphiprotic species (acting


as base or acid) depends on its dissociation
constants

HCO3(aq)
+ H 2 O(l) H 2 CO3(aq) + OH(aq)
2+
HCO3(aq)
+ H 2 O(l) CO3(aq)
+ H3O(aq)

K b2 = 2.38 x 10-8
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

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?

You accidentally spilled muratic acid (2.0 M HCl)


on the rubber flip-flops of your roommate. To
neutralize the acid, you looked for a base in the
dorm stock room, and you found two salts
sodium bicarbonate and sodium phosphate.
Which of the two salts will you use to quickly and
effectively neutralize the acid?

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)

3+
6 ( aq )

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

K a = 2.0 x 10-3

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

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)


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

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

Describe the direction of equilibrium shift


After adding 10.00 mL of 0.5 M HCl

+
CH3COOH(aq) + H 2O(l)
CH3COO(aq)
+ H3O(aq)

After adding 10.00 mL of 0.5 M NaCH3COO

(aq)

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

+ H 3O

+
(aq)

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


side that diminishes the added common/similar ion

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 pH of the final mixture
After adding 10.00 mL of 0.5 M HCl
DECREASE pH, more ACIDIC

After adding 10.00 mL of 0.5 M NaCH3COO


INCREASE pH, less ACIDIC

Buffers
Solutions that contain BOTH acid component and
its conjugate base
Conjugate base is present in the initial concentration
of components
Examples :
Acetic acid added with sodium acetate
Ammonium chloride added with aqueous ammonia solution

Solutions that resist drastic pH changes

Henderson-Hasselbalch Equation
Simplified equation for pH calculation involving
buffers

Henderson-Hasselbalch Equation
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

I
C
E

(aq)

+ H 2O (l)
C 4 H 4 O 3 COO

0.12 M
-x
0.12 - x

(x)(0.10 + x)
Ka =
(0.12 x)

(aq)

+
+ H 3 O (aq)

0.10 M
+x
0.10 + x

+x
x

(0.10)
pH = pK a +
(0.12)

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

Henderson-Hasselbalch Equation
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
 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

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

Neutralizing a liquid component with a strong opposite


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

Mixing two solid salts in the same volume of water


Ex. Solid NaH2PO4H2O and solid Na2HPO47H2O dissolved in
water (phosphate buffer)

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


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

pK a2 = 7.21

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

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

(100.0 mL)
moles H 2 PO + moles HPO =
(0.1 M)
(1000 mL )
1L
4

24

Common Ion Effect Buffers


Non-buffer Case: Consider the a solution of 50.00 mL of 0.05 M acetic
acid, CH3COOH.
Determine the pH of the solution.
Calculate the pH of the final mixture after adding 10.00 mL of 0.05 M HCl.
What is the pH?

 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.

CH 3 COOH

I
C

(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

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


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

Step 1: STOICHIOMETRIC 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)?


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

Buffer Capacity
 Amount of acid or base (usually in mL) needed to
change the pH of a buffer solution by 1 degree.




B number of moles of acid/base added per 1 L of buffer


solution
pH change in pH associated with the addition of
acid/base
B, pH, ,
Buffer capacity is highest when pH = pKa
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?

Acid-Base Neutralizations:
Indicators, Titrations
and
pH curves

Acid-Base Indicators
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 2 O ( l )

color 1
In (aq) + H 2 O ( l )
color a

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

Acidic indicator

color 2

HIn (aq)
+ OH (aq)

color b

Basic indicator

Acid-Base Indicators
The equilibrium constant expression for an indicator
would be expressed as:

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

[HIn]
[H3O ] = KIn [In ]
+

pH range when indicator


changes its color depends
largely on Ka of the indicator

Acid-Base Indicators
Color change ranges of some acid-base indicators

Indicator
Methyl violet
Methyl orange
Litmus
Phenolphthalein

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

Titration Curves
Strong Acid titrated with Strong Base
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:

Volume of
0.5 M NaOH
(mL)

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

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

Strong Acid/ Strong Base Titration Curve


SA-SB curve
14
13
12
11
10

Phenolphthalein

9
8
pH 7

Litmus

6
5
4

Methyl orange

3
2

Methyl violet

1
0
0

10

15
20
25
Volume Titrant (0.5 M NaOH)

30

35

40

Titration Curves
Weak Acid titrated with Strong Base
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:
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

15.00

7.5

5.0

7.5

40.0

4.921

20.00

10.0

2.5

10.0

45.0

5.348

25.00

12.5

12.5

50.0

9.071

30.00

15.0

12.5

55.0

12.658

WA-SB curve
14
13
12
11
10

Phenolphthalein

9
8
pH

Litmus

6
5
4

Methyl orange

3
2

Methyl violet

1
0
0

10

15

20
Titrant volume

25

30

35

40

WA vs SB Titration Curve Regions


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

WA-SB curve
14

Buffer Region: HH Equation


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

13
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])

9
8
pH

At half equivalence point:


pH = pKa

7
6
5
4

Initial Region: Use ICE


and Ka
pH = (pKa + pCHA)

3
2
1
0
0

10

15

20
Titrant volume

25

30

35

40

14
13
acetic curve

12

lactic curve

11

HClO curve

10

Phenolphthalein

9
8
7

Litmus

6
5
4

Methyl orange

3
2

Methyl violet

1
0
0

10

15

20

25

30

35

40

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?

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

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