Potentiometric Titration of

Acid-Base
(2016/03/12 revised)
Collect
 One 50 mL buret
 One 100 mL volumetric flask
 pH 7.00 and pH 4.00 standard buffer solution
(shared by two groups)
 Two 125 mL Erlenmeyer flasks (check if
broken)
 One pipet filler (check for gas leak)
 One magnetic stirring bar (from TA)
1
 Objective & Skills

I. Objective:
 To prepare and to standardize secondary-standard
solutions
 To determine the equivalence point of titration by using the
electric potential method
 To determine the dissociation constant of acetic acid, Ka

II. Skills:
 Learn to weigh chemicals and prepare solutions
 To operate volumetric flask, graduated pipet, and burets
 To calibrate and operate pH-meter
 To determine the equivalence point by using titration curves 2
 Standardization of Acid or Base
 Primary standard: larger molar mass and high purity
 Secondary standard: standardized acid or base
 Common primary standard acid:
potassium hydrogen phthalate (KHP)
 Common primary standard base:
sodium carbonate (Na2CO3)
 KHP is a monoprotic weak acid
The neutralization with NaOH takes place in a 1:1 ratio
HOOCC6H4COOK(aq) + NaOH(aq) 
C6H4(COO)22-(aq) + K+(aq) + Na+(aq) + H2O(l)

3
 Determine the Equivalence Point
• The pH value of the reacting solution changes significantly near the
equivalence point
• Base on the color change of the acid-base indicator or monitoring
the change in pH values to determine the equivalence point
14.00

Equivalence point
12.00

10.00
Acid pH Basic
Phenolphthalein Indicator
form range form
8.00

Methyl
pH

Bromothymol blue Red 3~4 Orange

6.00 orange
Bromothy-
4.00
Methyl orange Yellow 6~7 Blue
mol blue
2.00
Phenol- Pink
Colorless 8~10
0.00 phthalein red
0.00 10.00 20.00 30.00 40.00 50.00 60.00

NaOH滴定體積

4
Weak acid / strong base titration curve
 Acid-Base Indicator
 Acid-base indicator: a weak organic acid or base
 Weak acid (HIn) and its conjugate base (In－) with different
colors
HIn + H2O H3O+ + In－
Acidic Color Color Change Basic Color
HIn Range In－

pH increases
pKa － 1 pKa + 1

 Predict the pH range of the equivalence point

 Strong acid/weak base titration: pH < 7

 Weak acid/strong base titration: pH > 7

 Strong acid/strong base titration: pH = 7

 Choose the appropriate indicator to match the end-point with

5
the equivalence point
 10

Equivalence Point 8 Equivalence

point

pH
6

4
1. Acid-base titration curve
2
The equivalence point is the point 20 22 24
NaOH(aq) V (mL)
26

on the curve with the maximum 25

Equivalence
slope 20 point

△pH/△V
15
10
2. First derivative of titration curve 5
The maximum point is the 0
equivalence point 20 22 24 26
V1 (mL)
150
Equivalence A
100
3. Second derivative of the titration point

△2pH/△V2
50
curve 0
-50 20 22 24 26
0 crossing is the equivalence point
-100 B
-150 6
V2 (mL)
 Acid Dissociation Constant of
a Weak Acid
Ka 
A H O 

3

Weak acid – strong base
HA titration curve
 At Half-Equivalence point 14.00

[HA] ＝ [A-]
12.00

[H3O+] = Ka
Therefore, pH = pKa
10.00

For example 8.00

pH = pKa

pH
 Equivalence volume = 37.50 mL 6.00

 Half-equivalence volume = 18.75 mL

4.00

 V = 18.00, pH = 4.60
2.00
 V = 19.10, pH = 4.65 Half-equivalence volume
 pH of the half-equivalence volume = 4.63 0.00
0.00 10.00 20.00 30.00 40.00 50.00 60.00

 pKa = pH = 4.63 V (NaOH, mL)

 Ka = 2.3 × 10-5 7
 pH Meter
pH meter consists of three parts:
 pH electrode
 Reference electrode (usually made of silver and
silver chloride), the potential is a fixed value
 Indicator electrode (usually made of glass), the

potential changes when the concentration of H+

varies
 Thermoprobe: used to measure the temperature of soln
 Voltmeter: used to measure the potential difference
between the two electrodes

8
 Cell Potential and pH Value
Em = K − 2.3RT(pH)/nF
Em = mT(pH) + K
Second standard solution
First standard solution
The Relationship Between Measured
Cell Potential and pH value
 Em: measured cell potential
 K: constant, determined by the
type of electrode used
 R: gas constant
 T: absolute temperature of the
solution
 pH: pH value of solution
 n: number of moles of electrons
transferred through the
electrodes during a reaction
 F: Faraday constant
9
 Outline of Procedures
I. Prepare NaOH(aq) II. Standardization of III. Calibrate pH-meter
NaOH with KHP

IV. Titration of vinegar

10
 Procedure I. Prepare 0.1 M NaOH

(1) Take10 mL of 1 M NaOH

(2) Place in 100 mL volumetric flask
(3) Add water till mark to dilute

(1) Invert the flask

several times (1) Use approx. 5 mL
(2) Mix thoroughly of 0.1 M NaOH

(3) Pour into beaker (2) Rinse buret twice

and fill with solution
Read initial volume of
buret (Vi) to 0.01 mL
11
 Procedure II. Standardize NaOH
with KHP

(1) Dissolve with 50 mL

distilled water
(2) Add 2 d. of phenolphthalein
(3) Titrate with 0.1 M NaOH

 Measure ca. 0.2~0.22 g KHP

with analytical balance
 Titrate the solution to appear
 Place in a 125 mL
Erlenmeyer flask pink and persist for 30 s
 Record accurate weight  Record Vi and Vf
 Carry out a duplicate test
 Calculate average
concentration of NaOH
12
Procedure III. Calibrate the pH-meter
 Push the “POWER”
NT$ 4000 !! button, warm up for 10
minutes
 Remove the electrode cap
 Use washing bottle to
clean the electrodes
 Blot dry with a tissue
 Place electrode and
thermoprobe into solution

HOLD
Press “HOLD” when
cleaning the electrodes and
Setup of pH meter the screen will freeze
13
 Procedure III. Calibrate pH-meter
(1) Collect standard buffer solution
(2) Start calibrating pH meter

Slope
Calib button
button
pH 7.0 pH 4.0
 Immerse thermoprobe and electrodes  Clean thermoprobe and electrodes
into pH 7.00 buffer solution  Immerse in pH 4.00 buffer solution
 Adjust Calib button until meter says  Adjust Slope button until meter says
‘7.00’ ‘4.00’ 14
 Notice: Manipulate pH Meter
 The end of the electrode should be fully
immersed in the test solution and not
touching the walls of the container
 Do not take the electrode off of the holder
 Both thermoprobe and the electrode
should be placed in solution
 100 mL beakers are used for testing in
this experiment
 Position the electrode in the soln so that
the stirring bar will not strike the electrode
 Turn the magnetic stirring bar on during
titration
 Every time the testing solution is changed,
the electrode should be rinsed with
distilled water and blot dry with tissues
 When the electrode is not in use, it needs
to be immersed in clean distilled water
 When the electrode is not in use for long
periods of time, it should be immersed in 3
M KCl solution
15
 Procedure IV. Titration of Vinegar
Take sample:

(1) Transfer 3.0 mL vinegar (1) Add 40 mL distilled water

into a 100 mL beaker (2) 2 d. of phenolphthalein
(2) Record brand and (3) Place stirring bar, the electrode,
acidity of vinegar and thermoprobe in soln

 Titrate with standardized 0.1 M NaOH

Titrate  Add ~1 mL aliquots of NaOH and record Vi,
Vf, and pH value after each addition
 At pH 6~10: add titrant in 0.2 mL increments
 At pH > 10: add titrant in 1 mL increments
 When pH is ~12: stop titration

Setup of apparatus
 Observe and record the change in color of 16
solution during titration
 After Experiment

 Clean and check pH electrode

 Place electrode in plastic-cap that containing 3 M KCl
 Turn the pH meter off
 Hand in magnetic stirring bar
 Wash buret and invert to dip dry
 Waste liquids (salts) can be discarded in sin after
neutralization

17
 Data Analysis
 Calculate average standardized concentration of NaOH
 Calculate 3 equivalence pts and plot 3 graphs in Excel
 Calculate the molarity of acetic acid in vinegar (0.737 M)
N1V1 = N2V2
 Change into percent concentration and compare with labels
(assume density the same as water)
For example: 0.737 M × 60 /1000 × 1 g/cm3 × 100 % = 4.4 %
 Determine Ka of acetic acid from the half-equivalence point

18
 (15.10  16.15) (15.63  16.63)
Worksheet V1   15.63 V2   16.13
2 2
First derivative Second derivative
V NaOH pH V1 pH/V V2 (pH/V)/V1
15.10 4.99 15.63 0.09 16.13 0.02
16.15 5.08 16.63 0.11 17.11 0.02
17.10 5.18 17.60 0.12 18.14 0.03
18.10 5.30 18.68 0.16 19.21 0.05
19.25 5.48 19.75 0.21 20.23 0.11
20.25 5.69 20.70 0.31 21.14 0.46
21.15 5.97 21.58 0.72 21.84 8.25
22.00 6.58 22.10 5.05 22.20 22.50
22.20 7.59 22.30 9.55 22.40 -34.00
22.40 9.50 22.50 2.75 22.80 -3.00
22.60 10.05 23.10 0.95 23.60 -0.63
19
23.60 11.00 24.10 0.32 24.58 -0.14
 Graphs of the Titration of Vinegar
Titration curve

15.00

10.00
pH

5.00

0.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00
V(NaOH) First derivative

12.00
10.00
8.00

△pH/△V
6.00
4.00
2.00
0.00
-2.00 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00
V1 (NaOH)
Second derivative

40.00
△(△pH/△V)△V1

20.00

0.00
0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00
-20.00

-40.00
V2 (NaOH) 20