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: measured cell potential
Em = mT(pH) + K K: constant, determined by the
type of electrode used
R: gas constant
Second standard solution
T: absolute temperature of the
First standard solution solution
pH: pH value of solution
n: number of moles of electrons
transferred through the
electrodes during a reaction
F: Faraday constant
The Relationship Between Measured
Cell Potential and pH value
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
