PART 2

Outline
• Types of volumetric analysis
• Acid base titration
• Principle of acid base titration
•Term used (definition)
• Direct and back titration (involve calculation)
•pH and pOH
•Acid base titration Curve:
 Strong acid and strong base
Strong acid and weak base
Strong base and weak acid
Weak acid weak base
Calculation of pH change during strong acid-strong
base titration
Acid base indicators, choice of indicators
ACID-BASE TITRATION
CURVE
1. Titration ofstrong acid
with strong base.
2. Titration of strong acid
with weak base.
3. Titration of weak acid
with strong base.
4. Titration of weak acid
with weak base.
INDICATOR AND CHOICE OF INDICATOR
Acid –Base Indicators:
• The acid-base indicator function by changing colour just after
the equivalence point of a titration; this colour change is
called the end point.
• The end point is most often detected visually.
• Acid-base indicator are usually weak organic acids or bases
that dissociate partially in water with the undissociated
molecules have different color from their ions. (eg:
Undissociated molecule of phenolphthalein is colourless & it
anion is pink)
• Indicators can be monoprotic (HIn) or diprotic (H2In) acids.
• The acid form of an indicator is usually
coloured; when it loses a proton resulting in
anion (In-) , or base form of the indicator,
exhibiting different colour.
HIn  H+ + In-
(colour A) (colour B)

• A diprotic acid indicator, H2In ionizes in TWO steps as

follows…..
H2In  HIn- + H+  H+ + In-

(colour A) (colour B) (colour C)

 SELECTING AND USING
INDICATORS
 Choose an indicator that undergoes a distinct
colour change at the equivalence point (true end
point) of an acid-base titration .
 Choose an indicator whose middle half of the pH
transition range (greatest colour change)
encompasses/overlap the pH at the equivalence
point or the pH at the steepest part of the titration
curve.
 Indicators color change must be detectable by
normal eyesight. Choose the indicator which have
a rough tenfold excess of one or the other form
of the indicator must be present.
 Acid Base Indicators
COMMON TRANSITION COLOUR CHANGE
NAME RANGE ACID BASE
Crystal violet 0.1 – 1.5 Yellow Blue
Thymol blue 1.2 – 2.8 Red Yellow
Methyl yellow 2.9 – 4.0 Red Yellow
Methyl orange 3.1 – 4.4 Red Orange
Bromocresol green 3.8 – 5.4 Yellow Blue
Methyl red 4.2 – 6.3 Red Yellow
Chlorophenyl red 4.5 – 6.4 Yellow Red
Bromothymol blue 6.2 – 7.6 Yellow Blue
Phenol red 6.8 – 8.4 Yellow Red
Thymol blue 8.0 – 9.6 Yellow Blue
Phenolpthalein 8.3 – 10.0 Colourless Red
Alizarin yellow 10.0 – 12.0 Colourless Yellow
 CHOOSING A TITRANT
• In theory, any strong acid or strong base can be used as titrant.
• The reason for this is that most reaction involving a strong acid or a strong base
is quantitative.

ACID TITRANT
Strong Acid Titrant Weak Acid Titrant

• Hydrochloric acid (HCl) • Acetic acid (CH3COOH)

• Nitric acid (HNO3)
• Perchloric acid (HClO4)
• Phosphoric acid (H3PO4)
• Ammonium ion (NH4-)
• Hydrogen fluoride (HF)
• Carbonic acid (H2CO3)
• Nitrous acid (HNO2)
• Hydrogen sulphide (H2S)
• Hydrogen cyanide (HCN
 BASE TITRANT
Strong Base Titrant Weak Base Titrant
Sodium hydroxide, NaOH Ammonium hydroxide,
Potassium hydroxide, KOH NH4OH
Magnesium hydroxide, Amine acetate.
Mg(OH)2 Carbonate, CO32-
Barium hydroxide , Ba(OH)2 Fluoride ion,F-
Sodium carbonate,NaCO3
Acid- Base Titration
Curve
 Strong Acid-
Strong Base

Strong Base – ACID-BASE Weak Acid –

Weak Acid TITRATION Weak Base

Strong Acid -
Weak Base
 The Titration (or pH) Curve
• The change in pH during an acid-base titration can be
followed by measuring the pH of the mixture using a
pH meter
• The change is then plotted against the volume of
base (or acid) added from the burette
• These titration curves allow us to choose the most
suitable indicator for the particular titration
The Relationship Between pH & pOH
[H+][OH-]= Kw=1.0 x 10-14
-log [H+] – log [OH-] = 14.00
pH + pOH= 14.00

pH = -log [H+]

Solution Is At 250C
neutral [H+] = [OH-] [H+] = 1 x 10-7 pH = 7
acidic [H+] > [OH-] [H+] > 1 x 10-7 pH < 7
basic [H+] < [OH-] [H+] < 1 x 10-7 pH > 7

pH [H+]
 Strong acid with strong base
NaOH (aq) + HCl (aq) H2O (l) + NaCl (aq)

Buffer Region
• Sudden sharp changes of pH
• Salt formed: NaCl
• Neutral salt: So pH is 7

Slow change of pH

Titration curve for the titration of 25.00 mL of 0.20 M HCl with the 0.20 M NaOH
• Before addition of NaOH, the pH=1. As NaOH is added, the pH increases
gradually
• There is a sharp increase in pH (from 4 to 11) slightly before and after
equivalence point (pH=7)
• Beyond equivalence point, pH increases gradually as more NaOH added
• The suitable indicators are:

Indicator pH Range Colour Change

Methyl red 4.2 – 6.3 Red- Yellow
Chlorophenyl red 4.8 – 6.4 Yellow- Red
Bromothymol blue 6.0 – 7.6 Yellow- Blue
Phenol red 6.4 – 8.4 Yellow -Red
Cresol red 7.2-8.8 Yellow -Red
Phenolpthalein 8.3- 10.00 Colourless- pink
 Weak base with Strong acid
HCl (aq) + NH3 (aq) NH4Cl (aq)
At equivalence point (pH < 7):
NH4+ (aq) + H2O (l) NH3 (aq) + H+ (aq)

• Sharp rise in pH
• pH is less than 7
(usually around 5-6)
• Salt formed is acidic
• Before addition of HCl, the pH=11. When HCl is added, the pH
increases gradually as more NH3 neutralised and the solution
becomes more acidic.
• There is sharp decrease in pH (from 7 to 3) slightly before and
after equivalence point.
• Beyond equivalence point, pH decreases gradually as more
HCl is added
• The suitable indicators are:

Indicator pH Range Colour Change

Methyl Orange 3.1-4.4 Red-Yellow
Methyl Red 4.2-6.3 Red-Yellow
Chlorophenol blue 4.8-6.4 Yellow-Red
 Weak acid with Strong base
CH3COOH (aq) + NaOH (aq) CH3COONa (aq) + H2O (l)
At equivalence point (pH > 7):
CH3COO- (aq) + H2O (l) OH- (aq) + CH3COOH (aq)

• pH changes rapidly
• pH is higher than 7
(usually around 8-9)
• Salt formed is alkaline

18
• Before addition of NaOH, pH≈ 2.9 (ethanoic acid is a weak
acid). When NaOH is added, the pH increases gradually as
more CH3COOH is neutralised and the solution becomes less
acidic
• There is a sharp increase in pH (from 7 to 11) slightly before
and after equivalence point
• Beyond the equivalence point, the pH increases gradually as
more NaOH is added
• The suitable indicators are:
Indicator pH Range Colour Change
Cresol Red 7.2-8.8 Yellow-Red
Phenolpthalein 8.3- 10.00 Colourless- pink
 Weak Acid- Weak Base
• Titrations involving a weak acid with a weak base
are not normally done
• This is because the equivalence point cannot be
accurately observed
Calculation:
Titration Involving a Strong Acid & a Strong Base
NaOH (aq) + HCl (aq) → NaCl (aq) + H2O (l)
OH- (aq) + H+ (aq) → H2O (l)

1. When the NaOH is added

• pH increase slowly at first
2. Near the equivalence point (the point at which an
equimolar amount of acid and base have reacted)
• the curve rises almost vertically
3. Beyond the equivalence point
• pH increases slowly
Consider a titration of 50.00 mL of 0.500 M HCl with 0.100 M NaOH
(a) Determine the pH of solution before titration begins
-Before any base (NaOH) is added, the solution is 0.0500 M in H+ (0 mL of NaOH)
pH= -log [H+]= - log 0.0500= 1.30

(b) Determine the pH of solution after 10.00 mL of reagent (NaOH) is added:

- The H+ is decreased as a result of both reaction with the base and dilution. Thus, the
concentration analytical of HCl is
- CHCl= no of mmol HCl remaining after addition of NaOH
total volume of solution

= original no of mmol HCl – no of mmol of NaOH added

total volume of solution

= (50.00 mL x 0.0500 M) – (10.00 mL x 0.1000 M)

(50.00 + 10.00) mL

= (2.500 mmol – 1.000 mmol) = 2.500 x 10-2 M of HCl

60.00 mL

= CHCl= [H+], pH= -log [H+]= - log (2.500 x 10-2 ) = 1.602

(c) Equivalence point:
- At the equivalence point, neither HCl or NaOH is in excess. So, the concentration of H+
and OH- must be equal. Substituting this equality into the ion- product constant for
water (At the equivalence point, the solution is neutral and pH=7):
pKw= pH + pOH
-log 10-14= 14.00= pH + pOH
[H+ ]= √Kw = √1.00 x 10-14 = 1.00 x 10-7
pH= - log (1.00 x 10-7) = 7.00

(d) After addition of 25.00 mL of reagent (NaOH):

- The solution now contain an EXCESS of NaOH, and we can write
CNaOH= no of mmol added – no of mmol of HCl
total volume of solution

= (25.10 mL x 0.1000 M) – (50.00 mL x 0.050 M)

(50.00 + 25.00) mL

= 1.33 x 10-4 M of NaOH

• Beyond the equivalence point, we first calculate pOH and then pH.
* Remember that, pH= pKw- pOH = 14.00 – pOH

and the equilibrium concentration of OH- ion is:

[OH-]= CNaOH = 1.33 x 10-4 M of NaOH

pOH = -log (1.33 x 10-4)= 3.88,

and pH = 14.00 – 3.88 = 10.12

(e) Draw titration curve for the titration

(f) Determine the suitable indicator

- Alizarin yellow (pH: 10.0 – 12.0, Colourless (acid) turns to yellow (base))
DRAW A TITRATION CURVE FOR THE
REACTION BETWEEN 25 mL OF 0.2 M Ba(OH)2
AND 0.10 M HNO3
two (2) known quantities (volume and molarity are given) Y – axis
one (1) known quantity (volume or molarity is given) x – axis

y-axis -use to get the initial pH

Ba(OH)2  2OH- + Ba2+
0.2M 2(0.2) = 0.4  pOH = -log(0.4) = 0.398
pH = 14-0.398 = 13.6
x-axis -Ve
1Ba(OH)2 + 2HNO3  1Ba(NO3)2 + 2H2O
MaVa = a = 0.10 x Va= 2 , Va = 100 mL
MbVb b 0.20 x 25 1
 Draw titration curve
pH

13.6

Initial pH -------------------------

-----------------

0 Ve= 100mL
volume HNO3 added
…cont..eg
In an experiment 0.10M HCl is added to a conical flask containing
20 mL 0.10M NaOH solution.

HCl(aq) + NaOH(aq) -----> NaCl(aq) + H2O(l)

a) Calculate the pH of the NaOH(aq) before any HCl is added.

[note: the flask contains NaOH, a base solution.]

[OH-] = [NaOH] = 0.10 mol L-1

pOH = -log10[OH-] = -log10[0.10] = 1

pH = 14 - pOH = 14 - 1 = 13
 or the question is
Calculate the pH of the NaOH before any HCl is added and
draw a titration curve from the reaction.

two (2) known quantities (volume and molarity are given) Y – axis
one (1) known quantity (volume or molarity is given) x – axis

y-axis -use to get the initial pH

NaOH  OH- + Na+
0.1M 0.1M  pOH = -log(0.1) = 1
pH = 14-1 = 13
x-axis - Ve
1HCl + 1NaOH 1NaCl + 1H2O
MaVa = a = 0.10 x Va= 1 , Vb = 20 mL
MbVb b 0.10 x 20 1
 pH

Initial pH=13

------------------- equivalence point pH = 7

volume HCl added

0 Ve=20 mL

A strong base -strong acidtitration curve

 b) Calculate the pH of the solution in the conical flask(NaOH)
after the addition of 17.00 mL of the titrant (HCl)

[Note: Since the molarity of both HCl and NaOH are the same,
it is expected that 20 mL of HCl will be needed to neutralise 20
mL of NaOH]

mol of NaOH = 20/1000 x 0.1 = 2 x 10-3 mol

mol of HCl is added = 17/1000 x 0.1 = 1.7 x 10-3
mol total volume = 20.00 + 17.00 = 37.00 mL
mol excess = larger value – smaller value
= 2 x 10-3 – 1.7 x 10-3
= 3 x 10-4 mol OH-
new molarity [OH-] =3 x 10-4 = 8.11 x 10-3
37/1000
pOH = -log[OH-] = - log (8.11 x 10-3)
= 2.1
pH = 14 – 2.1 = 11.9
 Another technique

excess volume of NaOH = 20.00- 17.00 = 3 mL

mol of excess NaOH = 3 x 10-3 L x 0.1 mol/L = 3 x 10-4
total volume = 20.00 + 17.00 = 37.00 mL
new molarity of NaOH = 3 x 10-4 mol/ 0.037 L =8.11 x 10-3

pOH = -log[OH-] = - log (8.11 x 10-3)

= 2.1
pH = 14 – 2.1 = 11.9
c) Calculate the pH of the solution in the conical flask
after the addition of 22.00 mL of the titrant (HCl)
[ note:after the neutralization point; theflask contains HCl]
neutralization point only needed 20 mL of HCl]

mol of NaOH = 20/1000 x 0.1 = 2 x 10-3 mol

mol of HCl is added= 22/1000 x 0.1 = 2.2 x 10-3 mol
total volume = 20.00 + 22.00 mL= 42.00 mL
mol excess = larger value – smaller value
= 2.2 x 10-3 – 2 x 10-3 mol
= 2.0 x 10-4 mol
new molarity[H+] = 2 x 10-4 mol/ 0.042 L = 4.76 x 10-3

pH = -log[H-] = - log (4.76 x 10-3 )

= 2.32

pH = 2.32
 Another technique
excess volume of HCl = 22.00-20.00 mL= 2 mL
mol of excess HCl = 2 x 10-3 L x 0.1 mol/L = 2 x 10-4 mol
total volume = 20.00 + 22.00 mL= 42.00 mL
new molarity of HCl = 2 x 10-4 mol/ 0.042 L = 4.76 x 10-3

pH = -log[H-] = - log (4.76 x 10-3 )

= 2.32

pH = 2.32