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Potentiometric Titration of Acid-Base (2016/03/12 revised) Collect  One 50 mL buret  One 100
Potentiometric Titration of Acid-Base
Potentiometric Titration of
Acid-Base
Potentiometric Titration of Acid-Base (2016/03/12 revised) Collect  One 50 mL buret  One 100 mL

(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
Objective & Skills
Objective & Skills
Objective & Skills I. Objective:  To prepare and to standardize secondary-standard solutions  To determine

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, K a

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 
Standardization of Acid or Base
Standardization of Acid or Base
Standardization of Acid or Base  Primary standard: larger molar mass and high purity  Secondary

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 (Na 2 CO 3 )

KHP is a monoprotic weak acid

The neutralization with NaOH takes place in a 1:1 ratio

HOOCC 6 H 4 COOK (aq) + NaOH (aq)

C 6 H 4 (COO) 2 2- (aq) + K + (aq) + Na + (aq) + H 2 O (l)

3

Determine the Equivalence Point • The pH value of the reacting solu tion changes significantly
Determine the Equivalence Point
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 Phenolphthalein 8.00 Bromothymol blue 6.00 4.00 Methyl orange 2.00 0.00
14.00
Equivalence point
12.00
10.00
Phenolphthalein
8.00
Bromothymol blue
6.00
4.00
Methyl orange
2.00
0.00
0.00
10.00
20.00
30.00
40.00
50.00
60.00
NaOH滴定體積
pH

Weak acid / strong base titration curve

Acid pH Basic Indicator form range form Methyl Red 3~4 Orange orange Bromothy- Yellow 6~7
Acid
pH
Basic
Indicator
form
range
form
Methyl
Red
3~4
Orange
orange
Bromothy-
Yellow
6~7
Blue
mol blue
Phenol-
Pink
Colorless
8~10
phthalein
red

4

Acid-Base Indicator  Acid-base indicator: a weak organic acid or base  Weak acid (HIn)
Acid-Base Indicator
Acid-Base Indicator
Acid-Base Indicator  Acid-base indicator: a weak organic acid or base  Weak acid (HIn) and

Acid-base indicator: a weak organic acid or base

Weak acid (HIn) and its conjugate base (In ) with different colors

HIn + H 2 O

base (In - ) with different colors HIn + H 2 O H 3 O +

H 3 O + + In

Acidic Color HIn Color Change Range Basic Color In -
Acidic Color
HIn
Color Change
Range
Basic Color
In -

pH increases

pK a 1

pK a + 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 the equivalence point

5

pH/ V

10 Equivalence Point Equivalence 8 point 6 pH
10
Equivalence Point
Equivalence
8
point
6
pH
△ V 10 Equivalence Point Equivalence 8 point 6 pH 1. Acid-base titration curve The equivalence

1. Acid-base titration curve The equivalence point is the point on the curve with the maximum slope

2. First derivative of titration curve The maximum point is the equivalence point

4

2

25

20

15

10

5

0

3. Second derivative of the titration curve 0 crossing is the equivalence point

of the titration curve 0 crossing is the equivalence point 20 22 24 26 NaOH (aq)
of the titration curve 0 crossing is the equivalence point 20 22 24 26 NaOH (aq)
20 22 24 26 NaOH (aq) V (mL) Equivalence point 20 22 24 26
20
22
24
26
NaOH (aq) V (mL)
Equivalence
point
20
22
24
26

V 1 (mL)

150 Equivalence A 100 point 50 0 20 22 24 26 -50 -100 B -150
150
Equivalence
A
100
point
50
0
20
22
24
26
-50
-100
B
-150
6
V 2 (mL)
2 pH/ △ V 2
Acid Dissociation Constant of a Weak Acid K a   HA   A
Acid Dissociation Constant of a Weak Acid
Acid Dissociation Constant of
a Weak Acid
Acid Dissociation Constant of a Weak Acid K a   HA   A 

K a

HA

A



H O

3

 A   H O 3  

At Half-Equivalence point [HA] [A - ] [H 3 O + ] = K a Therefore, pH = pK a For example

Equivalence volume = 37.50 mL

Half-equivalence volume = 18.75 mL

V = 18.00, pH = 4.60

V = 19.10, pH = 4.65

pH of the half-equivalence volume = 4.63

pK a = pH = 4.63

K a = 2.3 × 10 -5

Weak acid – strong base titration curve 14.00 12.00 10.00 8.00 pH = pK a
Weak acid – strong base
titration curve
14.00
12.00
10.00
8.00
pH = pK a
6.00
4.00
2.00
Half-equivalence volume
0.00
0.00
10.00
20.00
30.00
40.00
50.00
60.00
V (NaOH, mL)
pH

7

pH Meter pH meter consists of three parts:  pH electrode  Reference electrode (usually
pH Meter
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

to measure the temperature of soln  Voltmeter: used to measure the potential difference between the

8

Cell Potential and pH Value E m = K − 2.3RT(pH)/nF E m = mT(pH)
Cell Potential and pH Value
Cell Potential and pH Value
Cell Potential and pH Value E m = K − 2.3RT(pH)/nF E m = mT(pH) +

E m = K 2.3RT(pH)/nF E m = mT(pH) + K

E m : 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

Second standard solution First standard solution
Second standard solution
First standard solution

The Relationship Between Measured Cell Potential and pH value

9

Outline of Procedures I. Prepare NaOH(aq) IV. Titration of vinegar II. Standardization of NaOH with
Outline of Procedures
Outline of Procedures

I. Prepare NaOH(aq)

Outline of Procedures I. Prepare NaOH(aq) IV. Titration of vinegar II. Standardization of NaOH with KHP

IV. Titration of vinegar

of Procedures I. Prepare NaOH(aq) IV. Titration of vinegar II. Standardization of NaOH with KHP III.

II. Standardization of NaOH with KHP

Procedures I. Prepare NaOH(aq) IV. Titration of vinegar II. Standardization of NaOH with KHP III. Calibrate
Procedures I. Prepare NaOH(aq) IV. Titration of vinegar II. Standardization of NaOH with KHP III. Calibrate

III. Calibrate pH-meter

Procedures I. Prepare NaOH(aq) IV. Titration of vinegar II. Standardization of NaOH with KHP III. Calibrate

10

Procedure I. Prepare 0.1 M NaOH (1) Take10 mL of 1 M NaOH (2) Place
Procedure I. Prepare 0.1 M NaOH (1) Take10 mL of 1 M NaOH (2) Place
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 (2) Mix thoroughly

(1) Invert the flask several times (2) Mix thoroughly (3) Pour into beaker (1) Use approx.

(3) Pour into beaker

(1) Use approx. 5 mL of 0.1 M NaOH

(3) Pour into beaker (1) Use approx. 5 mL of 0.1 M NaOH (2) Rinse buret

(2) Rinse buret twice and fill with solution

5 mL of 0.1 M NaOH (2) Rinse buret twice and fill with solution Read initial
5 mL of 0.1 M NaOH (2) Rinse buret twice and fill with solution Read initial

Read initial volume of buret (V i ) to 0.01 mL

11

Procedure II. Standardize NaOH with KHP (1) Dissolve with 50 mL distilled water (2) Add
Procedure II. Standardize NaOH with KHP
Procedure II. Standardize NaOH
with KHP
Procedure II. Standardize NaOH with KHP (1) Dissolve with 50 mL distilled water (2) Add 2
Procedure II. Standardize NaOH with KHP (1) Dissolve with 50 mL distilled water (2) Add 2

(1) Dissolve with 50 mL distilled water

NaOH with KHP (1) Dissolve with 50 mL distilled water (2) Add 2 d. of phenolphthalein

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

Measure ca. 0.2~0.22 g KHP with analytical balance

Place in a 125 mL Erlenmeyer flask

Record accurate weight

in a 125 mL Erlenmeyer flask  Record accurate weight  Titrate the solution to appear

Titrate the solution to appear pink and persist for 30 s

Record V i and V f

Carry out a duplicate test

Calculate average concentration of NaOH

12

Procedure III. Calibrate the pH-meter NT$ 4000 !! Setup of pH meter HOLD Press “HOLD”
Procedure III. Calibrate the pH-meter
Procedure III. Calibrate the pH-meter
Procedure III. Calibrate the pH-meter NT$ 4000 !! Setup of pH meter HOLD Press “HOLD” when
NT$ 4000 !!
NT$ 4000 !!

Setup of pH meter

III. Calibrate the pH-meter NT$ 4000 !! Setup of pH meter HOLD Press “HOLD” when cleaning

HOLD

Press “HOLD” when cleaning the electrodes and the screen will freeze

Push the “POWERbutton, 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

13

Procedure III. Calibrate pH-meter (1) Collect standard buffer solution (2) Start calibrating pH meter Calib
Procedure III. Calibrate pH-meter
Procedure III. Calibrate pH-meter
Procedure III. Calibrate pH-meter (1) Collect standard buffer solution (2) Start calibrating pH meter Calib button

(1) Collect standard buffer solution (2) Start calibrating pH meter

Calib button
Calib
button

pH 7.0

Immerse thermoprobe and electrodes into pH 7.00 buffer solution

Adjust Calib button until meter says

7.00

Slope button
Slope
button

pH 4.0

Clean thermoprobe and electrodes

Immerse in pH 4.00 buffer solution

Adjust Slope button until meter says

4.00

14

Notice: Manipulate pH Meter  The end of the electrode should be fully immersed in
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
Take sample: (1) Transfer 3.0 mL vinegar (1) Add 40 mL distilled water into a
Take sample: (1) Transfer 3.0 mL vinegar (1) Add 40 mL distilled water into a
Take sample: (1) Transfer 3.0 mL vinegar (1) Add 40 mL distilled water into a
Take sample:
Take sample:
Take sample: (1) Transfer 3.0 mL vinegar (1) Add 40 mL distilled water into a 100

(1) Transfer 3.0 mL vinegar

(1)

Add 40 mL distilled water

into a 100 mL beaker

(2)

2 d. of phenolphthalein

into a 100 mL beaker (2) 2 d. of phenolphthalein (2) Record brand and acidity of

(2) Record brand and acidity of vinegar

Titrate

(2) Record brand and acidity of vinegar Titrate Setup of apparatus Procedure IV. Titration of Vinegar

Setup of apparatus

Procedure IV. Titration of Vinegar

Setup of apparatus Procedure IV. Titration of Vinegar (3) Place stirring bar, the electrode, and thermoprobe

(3) Place stirring bar, the electrode,

and thermoprobe in soln

Titrate with standardized 0.1 M NaOH

Add ~1 mL aliquots of NaOH and record V i , V f , 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

Observe and record the change in color of solution during titration

16

After Experiment  Clean and check pH electrode  Place electrode in plastic-cap that containing
After Experiment
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

bar  Wash buret and invert to dip dry  Waste liquids (salts) can be discarded

17

Data Analysis  Calculate average standardized concentration of NaOH  Calculate 3 equivalence pts and
Data Analysis
Data Analysis
Data Analysis  Calculate average standardized concentration of NaOH  Calculate 3 equivalence pts and plot

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)

N 1 V 1 = N 2 V 2

Change into percent concentration and compare with labels

(assume density the same as water)

For example: 0.737 M × 60 /1000 × 1 g/cm 3 × 100 % = 4.4 %

Determine K a of acetic acid from the half-equivalence point

18

Worksheet

(15.10 16.15)    15.63 V 1 2
(15.10 16.15)
 15.63
V 1
2

(15.63 16.63)

V 2

16 . 13

2

First derivative Second derivative pH V pH/V V (pH/V)/V 1 V NaOH 1 2 15.10
First derivative
Second derivative
pH
V
pH/V
V
(pH/V)/V 1
V NaOH
1
2
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
23.60
11.00
24.10
0.32
24.58
-0.14

19

Graphs of the Titration of Vinegar

Titration curve 15.00 10.00 5.00 0.00 0.00 5.00 10.00 15.00 20.00 25.00 30.00 35.00 V(NaOH)
Titration curve
15.00
10.00
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
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
20.00
0.00
0.00
5.00
10.00
15.00
20.00
25.00
30.00
35.00
-20.00
-40.00
20
V2 (NaOH)
△(△pH/△V)△V1
pH
△pH/△V