standard solution

 Titration
 Volumetric analysis – technique
for determining the amount of a
certain substance by doing a
titration
 Analytical method in which a
standard solution of known
concentration (titrant) is used to
determine the concentration of
an unknown solution (analyte)

unknown solution
 Equivalence point (endpoint)
 Point at which equal amounts
of H3O+ and OH- have been
added.
 Determined by:
 indicator color change
• dramatic change in pH
moles H3O = moles OH
+ -

MV n = MV n
M: Molarity / concentration
V: volume
n: # of H+ ions in the acid
or OH- ions in the base
  42.5 mL of 1.3M KOH are required to neutralize
50.0 mL of H2SO4. Find the molarity of H2SO4.

H3O+ OH- MVn = MVn

M=? M = 1.3M M(50.0mL)(2)
V = 42.5 mL =(1.3M)(42.5mL)(1)
V = 50.0 mL
n=2 n=1 M = 0.55M H2SO4
Courtesy Christy Johannesson [Link]/communicationsarts/pages/chem
If 0.1M NaOH is added dropwise to 20 cm3 of 0.1M HCl (2 x 10-3 moles), the change
in pH of the solution can be calculated by considering the reaction taking place.

Before the addition of NaOH, the pH of the solution is 1.0.

[H3O+] = 5 x 10-6 = 1.25 x 10-4 M pH = 3.9
0.03995
Consider the titration of 50.0 mL of 0.100 M acetic acid, HC2H3O2, with
0.100 M NaOH

The initial pH—This pH is just the pH of the 0.100 M HC2H3O2. The

calculated pH of 0.100 M HC2H3O2 is 2.89.

Between the initial pH and the equivalence point—To determine pH in

this range, we must consider the neutralization of the acid:

Before reaching the equivalence point, part of the HC2H3O2 is neutralized to

form C2H3O2–. Thus, the solution contains a mixture of HC2H3O2 and C2H3O2–.
25 mL of 0.10 M NaOH has been added

0.025
Equal at the
halfway point
The solution now contains a mixture of a weak acid (CH3COOH) and its conjugate
base (CH3COO-). It thus behaves as a buffer solution. The pH of the mixture can
thus be calculated by considering the relative concentrations of the CH3COOH and
CH3COO.

Ka = [H3O+][CH3COO-] so [H3O+] = Ka[CH3COOH] = 1.7 x 10-5 M and pH = 4.8

[CH3COOH] [CH 3COO-]
 pH curves
The Progress of an acid-base titration is often
monitored by plotting the pH of the solution being
analysed as a function of the amount of titrant added.
Such a plot is called a pH curve or titration curve.

Types There are four types of acid-base titration; each

has a characteristic curve.

strong acid (HCl) v. strong base (NaOH)

weak acid (CH3COOH) v. strong alkali (NaOH)

strong acid (HCl) v. weak base (NH3)

weak acid (CH3COOH) v. weak base (NH3)

 In the following examples, alkali (0.1M) is
added to 25cm3 of acid (0.1M)

End points need not be “neutral‘ due to the

phenomenon of salt hydrolysis
Solution
of NaOH
OH-
Na+ Na+
OH- OH-
Na+ Na+
OH-

Solution
of HCl H+ Cl
Cl- H+
H+
H+ Cl-
Cl-
pH 1 at the start
due to 0.1M HCl
(strong
monoprotic acid)
 Very little pH change
during the initial 20cm3
pH 1 at the start
due to 0.1M HCl
(strong
monoprotic acid)
 Very sharp change in pH
over the addition of less
than half a drop of NaOH

Very little pH change

during the initial 20cm3
pH 1 at the start
due to 0.1M HCl
(strong
monoprotic acid)
 Curve levels off at pH 13
due to excess 0.1M NaOH
(a strong alkali)

Very sharp change in pH

over the addition of less
than half a drop of NaOH

Very little pH change

during the initial 20cm3
pH 1 at the start
due to 0.1M HCl
(strong
monoprotic acid)
Titration of alkaline added to acid and acid added to alkaline
 Curve levels off at pH 13
due to excess 0.1M NaOH
(a strong alkali)

Sharp change in pH over

the addition of less than
half a drop of NaOH

Steady pH change

pH 4 due to 0.1M
CH3COOH (weak
monoprotic acid)
 Curve levels off at pH 10
due to excess 0.1M NH3
(a weak alkali)

Sharp change in pH over

the addition of less than
half a drop of NH3

Very little pH change

during the initial 20cm3
pH 1 at the start
due to 0.1M HCl
 Curve levels off at pH 10
due to excess 0.1M NH3
(a weak alkali)

NO SHARP
Steady pH change CHANGE IN pH
 The titration curves for all the different possible titrations can be
sketched on the same graph as follows:

Type of pH at end- pH change at

titration point end-point
Strong acid - 7.0 4 to 10
strong alkali
Weak acid - Approx 8.5 7 to 10
strong alkali
Strong acid - Approx 5.5 4 to 7
weak alkali
Weak acid - Approx 7 No sudden
weak alkali change
 Acids like sulfuric acid (H2SO4) and phosphoric acid
(H3PO4), can dissociate more than one proton and are
called polyprotic acids.
 They dissociate in a stepwise manner.
Example: (H2CO3)
H2CO3(aq) ∏ H +(aq) + HCO3-(aq) Ka1 = [H+] [HCO-]
[H2CO3 ]
= 4.3 x 10
- + 2- + 2-
HCO3 (aq) ∏ H [aq] + CO3 (aq) Ka2 = [H ][CO3 ]
-
- [HCO ]
-11
=5.6 x 10
Ka1 > Ka2
The acid in each step is weaker
Sodium carbonate reacts with hydrochloric acid in two steps...
Step 1 Na2CO3 + HCl ——> NaHCO3 + NaCl
Step 2 NaHCO3 + HCl ——> NaCl + H2O + CO2
Overall Na2CO3 + 2HCl ——> 2NaCl + H2O + CO2

There are two sharp pH changes

The second addition of HCl is exactly

the same as the first because the
number of moles of HCl which react
with the NaHCO3 is the same as that
reacting with the Na2CO3.

17.50cm3 35.00cm3
 Other pH curves - polyprotic acids (H3PO4)

Phosphoric acid is triprotic; it reacts with sodium hydroxide in three steps...

Step 1 H3PO4 + NaOH ——> NaH2PO4 + H2O
Step 2 NaH2PO4 + NaOH ——> Na2HPO4 + H2O
Step 3 Na2HPO4 + NaOH ——> Na3PO4 + H2O

pH of Na3PO4 = 12

pH of Na2HPO4 = 9.6

pH of NaH2PO4 = 4.4

pH of H3PO4 = 1.5
 Acid-Base indicators

There are two common methods for determining the

equivalence point of an acid-base titration:

•Use a pH meter
•Use an acid-base indicator which marks the end point of a
titration by changing colour.
General Many indicators are weak acids and partially dissociate in aqueous
solution
HIn(aq) Ý H+(aq) + In¯(aq)

The un-ionised form (HIn) is a different colour to the anionic form (In¯).

Apply Le Chatelier’s Principle to predict any colour change

In acid - increase of [H+]

- equilibrium moves to the left to give red undissociated form

In alkali - increase of [OH¯]

- OH¯ ions remove H+ ions to form water; H+(aq) + OH¯(aq) Ý H2O(l)
- equilibrium will move to the right to produce a blue colour

Summary In acidic solution

HIn(aq) Ý H+(aq) + In¯(aq)

In alkaline solution
 The pH at which these transitions will occur depends on
the KIn of the indicator.

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

[HIn] [In -]

 Where KIn is the acid dissociation constant for the

indicator
 If [H3O+] > 10 x KIn, then [HIn]/[In-] > 10 and colour 1
(red) dominates.
 If [H3O] < 0.1 x KIn, then [Hin]/[In-] < 0.1 and colour 2
(blue) dominates.
 At intermediate H3O+ concentrations, neither colour
dominates.
 The equivalence point of a titration is where
you have mixed the two substances in exactly
equation proportions.
 You need to choose an indicator which changes
colour as close as possible to that equivalence
point.
 That varies from titration to titration.
• The indicator must change within the
vertical portion of the pH curve
• Neither indicator changes colour at the
equivalence point.
• Because the graph is so steep at that
point that there will be virtually no
difference in the volume of acid added
whichever indicator you choose.
However, it would make sense to titrate (20.00
to mL of 0.500 M HCl by 0.500 M NaOH)
the best possible colour with each 14.0
indicator. 12.0
If you use phenolphthalein, you would Color change
10.0 alizarin yellow R
titrate until it just becomes colourless (at Color change
pH 8.3) because that is as close as you 8.0 phenolpthalein
equivalence Color change

pH
can get to the equivalence point. point bromthymol blue
6.0
On the other hand, using methyl orange,
4.0 Color change
you would titrate until there is the very first bromphenol blue
trace of orange in the solution. If the Color change
2.0 methyl violet
solution becomes red, you are getting
0.0
further from the equivalence point. 0.0 10.0 20.0 30.0
Volume of 0.500 M NaOH added
(mL)
• Methyl orange will change sharply at the equivalence point
• Phenolpthalein will not be used
 Methyl orange is not suitable
 phenolphthalein changes sharply at the
equivalence point.
• Neither indicators are suitable
• An indicator requires a vertical portion of the curve over about two pH
units at the equivalence point to give a sharp shange.
• On the whole, you would never titrate a weak acid and a weak base in
the presence of an indicator.
7. What is the pH of a solution made by dissolving 2.5 g NaOH in 400 mL water?
Determine number of moles of NaOH

 1 mol NaOH 
x mol NaOH = 2.5 g NaOH    0.0625 mol NaOH
 40 g NaOH 
Calculate the molarity of the solution

mol 0.0625 mol NaOH

M  [Recall 1000 mL = 1 L]
L 0.4 L

MNaOH = 0.15625 molar

NaOH Na1+ + OH1-

0.15625 molar 0.15625 molar 0.15625 molar

pOH = -log [OH-] or kW = [H+] [OH-]

pOH = -log [0.15625 M] 1 x 10-14 = [H+] [0.15625 M]
pOH = 0.8 [H+] = 6.4 x 10-14 M
pOH + pH = 14 pH = -log [H+]
0.8 + pH = 14 pH = 13.2 pH = -log [6.4 x 10-14 M]
What volume of 0.5 M HCl is required to titrate 100 mL of 3.0 M Ca(OH) 2?

"6.0 M"
2 HCl + Ca(OH)2 CaCl2 + 2 HOH
x mL 100 mL
0.5 M 3.0 M

M1V1 = M2V2 M1V1 = M2V2

(0.5 M) (x mL) = (3.0 M) (100 mL) (0.5 M) (x mL) = (6.0 M) (100 mL)
x = 600 mL of 0.5 M HCl x = 1200 mL of 0.5 M HCl

HCl Ca(OH)2
mol molHCl = MxL molCa(OH) = M x L
2

M L mol = (0.5 M)(0.6 L) mol = (3.0 M)(0.1 L)

mol = 0.3 mol HCl mol = 0.3 mol Ca(OH)2

HCl H1+ + Cl1- Ca(OH)2 Ca2+ + 2OH1-

0.3 mol 0.3 mol 0.3 mol 0.3 mol 0.3 mol 0.6 mol

[H+] = [OH-]
6. 10.0 grams vinegar titrated with 65.40 mL of 0.150 M NaOH
(acetic acid + water)

A) moles HC2H3O2 = moles NaOH mol

M L
NaOH
molNaOH = M x L

therefore, you have ... mol = (0.150 M)(0.0654 L)

0.00981 mol HC2H3O2 mol = 0.00981 mol NaOH

 60 g HC3H2O2 
B) x g HC2H3O2 = 0.00981 mol HC2H3O2    0.59 g HC2H3O2
 1 mol HC3H2O2 
part 
C) % =   x 100%
 whole 
 0.59 g acetic acid 
% =   x 100%
 10.0 g vinegar 
% = 5.9 % acetic acid
Commercial vinegar is sold as 3 - 5 % acetic acid
?
1.0 M HCl titrate with ? M NaOH
1.00 mL 2.00 mL

M1 V1 = M2 V2
(1.0 M)(1.00 mL) = (x M)(2.00 mL)
X = 0.5 M NaOH
2.0 M H 1+

1.0 M H2SO4 titrate with ? M NaOH

1.00 mL 2.00 mL

M1 V1 = M2 V2
(1.0 M)(1.00 mL) = (x M)(2.00 mL)
X = 0.5 M NaOH