CH3340E: Quantitative Analysis

Dr. Vu Anh Tuan

 Acid-Base Titrations
Part I. Preparation the primary standard solution (0.1 N
borax)

Part II Preparation the approximately 0.1 N hydrochloric

acid solution

Part III. Standardization the solution of hydrochloric acid

Part IV. Quantitative determination of sodium hydroxide

with two indicators

Part V. Quantitative determination of sodium hydroxide

and sodium carbonate in a mixture.
 Part I. Preparation the primary standard solution (0.05 M
borax)

1. Calculate a primary standard sample (mB) for

preparation 250 mL (V) of solution.
2. Weigh accurately borax sample (~4.7 g) on
analytical balance. record the mass to a
precision of ± 0.0001 g.
3. Transfer the borax into 250-mL volumetric
flask by a funnel and hot distilled water and
then dilute with distilled water to the reference
line and mix well.
4. Calculate precision concentration of prepared
solution of borax.
 Part II. Preparation the approximately 0.1 N hydrochloric acid
solution

1.Calculate volume of 37% concentrated hydrochloric

acid sample VAconc (mL) for preparation of 500 mL of
solution.

2. Measure concentrated hydrochloric acid aliquot in a

graduated cylinder, transfer it into 500-mL beaker
containing about 500 mL of distilled water and mix
well by your stirring rod. This step must be done in a
fume hood
Part III. Standardization the solution of hydrochloric acid

Background
Titration reaction:

At the neutralization point (or equivalence point: the point when all the
liberated OH- have been converted to H2O) the solution will be slightly
acidic:

Thus, the appropriate indicator for this acid base titration is methyl red,
indicator pH range: 4.2 – 6.3
Experiment
1. Load a burette with prepared hydrochloric
acid solution.
2. Pipet a 10.0 mL aliquot of standard borax
solution (VB) into a 100-mL conical flask.
3. Add 2-3 drops of methyl red indicator, and
titrate with prepared hydrochloric acid solution
until the solution changes color from yellow to
red. Read the burette mark.
4. Repeat titration also two times. Calculate the
median volumes of the used hydrochloric acid
solution (VA).
5. Calculate the exact concentration of the
hydrochloric acid solution accordance to
equivalents law:
NA = NB⋅VB/VA
 Part IV. Quantitative determination of sodium
hydroxide

Background
• This type of reaction is a neutralization reaction, where salt and
water are products of the reaction:

NaOH + HCl = NaCl + H2O

• The change in pH in the equivalence-point region is large, ∆pH: 9.7 –

4.3.

• Methyl red (indicator pH range: 4.2 – 6.3) and phenolphthalein

(indicator pH range: 8.3 – 10.0) could be used as acid-base
indicators
Experiment procedures
Phenolphthalein Methyl red
1. Load a burette with prepared 1. Load a burette with prepared
hydrochloric acid solution. hydrochloric acid solution.
2. Pipet a 10.0 mL aliquot of sodium 2. Pipet a 10.0 mL aliquot of sodium
hydroxide sample (VNaOH) into a 100- hydroxide sample (VNaOH) into a 100-
mL conical flask. mL conical flask.
3. Add 7-8 drops of phenolphthalein 3. Add 2-3 drops of methyl red
indicator, and titrate with prepared indicator, and titrate with prepared
hydrochloric acid solution until the hydrochloric acid solution until the
solution lost the red color. solution changes color from yellow to
red.
4. Repeat titration two times.
Calculate the median volumes of 4. Repeat titration two times. Calculate
used hydrochloric acid solution (VHCl). the median volumes of used
hydrochloric acid solution (VHCl).
5. Calculate the concentration of
sodium hydroxide sample in M and 5. Calculate the concentration of
g/l sodium hydroxide sample in M and g/l
Quantitative determination of sodium hydroxide and
sodium carbonate in a mixture
I. Direct titration the mixture of sodium hydroxide and
sodium carbonate Background

NaOH + HCl = NaCl + H2O (1) HCl

Na2CO3 + HCl = NaHCO3 + NaCl (2)

NaHCO3 + HCl = H2CO3 + NaCl (3)

pH value of the solution at the first equivalence point:

pH = 1/2(pKa1 + pKa2) = 8.34

Titration with hydrochloric acid to a phenolphthalein end point

(Vphth):

pH value of the solution at the second equivalence point:

pH = ½(pKa1 + lg[H2CO3]) = ½(6,35 + 4) = 5.18
Titration with hydrochloric acid to a methyl NaOH,
orange end point (Vmo):
Na CO
 Methyl orange Phenolphtaleine

In a solution becoming less acidic,

methyl orange changes from red to
orange and, finally, to yellow
Experimental Procedure
1. Load a burette with prepared hydrochloric acid solution.
HCl Vphth

Vmo
2. Pipet a 10.0 mL aliquot of mixture sample (VS) into 100-mL
conical flask.

3. Add 7-8 drops of phenolphthalein indicator, and titrate with

prepared hydrochloric acid solution until the solution lost the red
color. Read the first burette mark (Vphth).

4. Continuously add 2-3 drops of methyl orange solution, and

titrate with prepared hydrochloric acid solution until the solution
changes color from yellow to yelloworange. Read the second
burette mark (Vmo).

6. Repeat the titration procedure also two times. Calculate the

median volumes of used hydrochloric acid solution Vphth and (VS)
Vmo.

7. Calculate the concentration of sodium hydroxide and sodium NaOH,

carbonate in the mixture sample in M and g/l. Na2CO3
 𝟐𝐕𝐩𝐡𝐭𝐡 −𝐕𝐦𝐨 ×𝐂𝐌(𝐇𝐂𝐥)
CM (NaOH) =
𝐕𝐒

𝐕𝐦𝐨 −𝐕𝐩𝐡𝐭𝐡 ×𝐂𝐌(𝐇𝐂𝐥)

CM (Na2CO3) =
𝐕𝐒

CM (HCl) = 0.1 M
VS = 10 mL
II. Back-titration the mixture of sodium hydroxide and sodium carbonate

Background

Sodium hydroxide and sodium carbonate can be accurately determined in

mixture by first titration with hydrochloric acid to a methyl orange end point
(Vmo):

NaOH + HCl = NaCl + H2O (1)

Na2CO3 + HCl = NaHCO3 + NaCl (2)

NaHCO3 + HCl = H2CO3 + NaCl (3)

Secondly, precipitation of carbonate ion with barium chloride:

Na2CO3 + BaCl2 = BaCO3 + 2NaCl

Then titration with hydrochloric acid to a phenolphthalein end point (Vphth):

NaOH + HCl = NaCl + H2O

 Experimental procedure
1. Load a burette with prepared hydrochloric acid solution.

2. Pipet a 10.0 mL aliquot of mixture sample (VS) into 100-mL conical flask.

3. Add 2-3 drops of methyl orange indicator, and titrate with prepared
hydrochloric acid solution until the solution changes color from yellow to yellow-
orange. Read the burette mark (Vmo).

4. Repeat titration also two times. Calculate the median volumes of the used
hydrochloric acid solution (Vmo).

5. Refill the burette with prepared hydrochloric acid solution.

6. Pipet a 10.0 mL aliquot of mixture sample (VS) into 100-mL conical flask.

7. Add 5-7 mL of 5 % barium chloride solution.

8. Add 7-8 drops of phenolphthalein indicator, and titrate with prepared

hydrochloric acid solution until the solution lost the red color. Read the burette
mark (Vphth).
9. Repeat titration also two times. Calculate the median volumes of used
hydrochloric acid solution (Vphth).

10. Calculate the concentration of sodium hydroxide and sodium carbonate in

the mixture sample in M and g/l
 𝐕𝐩𝐡𝐭𝐡 ×𝐂𝐌(𝐇𝐂𝐥)
CM (NaOH) =
𝐕𝐒

𝐕𝐦𝐨 −𝐕𝐩𝐡𝐭𝐡 ×𝐂𝐌(𝐇𝐂𝐥)

CM (Na2CO3) =
𝟐×𝐕𝐒

CM (HCl) = 0.1 M
VS = 10 mL
Any Questions??
 Redox Titrations
• Part I. Preparation of the primary standard solution
0.05N H2C2O4

• Part II. Standardization of KMnO4 solution

• Part III. Quantitative determination of ferrous

solution
 Background
KMnO4
• The redox reaction:
2KMnO4 + 5 H2C2O4 + 2H2SO4 = 2MnSO4 + 10CO2 + K2SO4 + 8H2O
• Potassium permanganate, KMnO4, is a strong oxidizing agent.
Permanganate, MnO4- is an intense dark purple color.
• Reduction of purple permanganate ion to the colorless Mn2+ ion,
the solution will turn from dark purple to a faint pink color at the
equivalence point. No additional indicator is needed for this
titration.
• The reduction of permanganate requires strong acidic conditions.
In this experiment, permanganate will be reduced by oxalic acid,
H2C2O4 in acidic conditions.
• Oxalic acid reacts very slowly at room temperature so the
solutions are titrated at hot to make the procedure practical.

H2C2O4,
H2SO4 6N,
Temperature of 70 oC
Part I. Preparation of the primary standard solution
0.05N H2C2O4

1. Calculate a primary standard sample:

mB = N x(V/1000) x meqo

2. Weigh accurately oxalic acid sample (~ 0.7 g)

3. Add 30-40 mL of warm distilled water to the beaker (or gently heat the
beaker), dissolve oxalic acid using a stirring rod.

4. Transfer the oxalic acid solution via your stirring rod into 250-mL
volumetric flask, and dilute with distilled water to the reference line and
mix well.

5. Calculate precision concentration of the prepared solution of oxalic

acid.
Part II. Standardization of KMnO4 solution

1. Load a burette with KMnO4 solution.

2. Pipet a 10.0 mL aliquot of standard oxalic acid solution into 100-mL

conical flask, add 5-7 ml of 6N H2SO4.

3. Heat acidified solution to about 80 oC. Do not boil the solution.

4. Slowly titrate the hot oxalic acid solution with few drops of the
KMnO4 solution at the beginning. Then, titrate until the appearance of
a faint pink color (persists for at least 30s). Read the burette mark.

4. Repeat titration also two times. Calculate the median volumes of the
used KMnO4 solution.

5. Calculate the exact concentration of KMnO4.

Part III. Quantitative determination of ferrous solution
KMnO4
Background
Redox reaction:

2KMnO4 + 10FeSO4 + 8H2SO4 = 5Fe2(SO4)3 + 2MnSO4 + K2SO4 + 8H2O

✓ The reduction of permanganate requires strong acidic conditions

✓ Phosphoric acid will be used to ensure that the ferric product, Fe3+
remains in its colorless form: [Fe(HPO4- ) ]+ colorless

Fe2+,
H2SO4 and H3PO4
Room temperature
Without H3PO4
Titration procedure

1. Load a burette with KMnO4 solution.

2. Pipet a 10.0 mL sample of the unknown Fe2+ solution into a 100-mL

Erlenmeyer flask.

3. Add 5-7 ml of a mixture of H2SO4 + H3PO4.

4. Titrate the sample with the KMnO4 solution until the appearance of
a faint pink color (persists for at least 30s). Read the burette mark.

5. Repeat titration also two times. Calculate the median volumes of the
used KMnO4 solution.

6. Calculate the exact concentration of the Fe2+ solution.

 Precipitation Titrations
• Part I. Morh’s method
• Part II. Fajan’s method

In this laboratory exercise, we will analyze a sample of Butter for its Chloride Ion
(Cl-) content
Part I. Morh’s method
AgNO3

❖The Mohr method uses chromate ions as an

indicator in the titration of chloride ions with a silver
nitrate standard solution. K2CrO4

❖ After all the chloride has been precipitated as white

silver chloride, the first excess of titrant results in
the formation of a silver chromate precipitate, which
signals the end point.
NaCl

brick-red
Experimental procedure

1. Load a burette with

standard 0.05M AgNO3
solution.
2. Pipet a 10.0 mL sample of
the unknown Cl- solution into
a 100 mL Erlenmeyer flask.
3. Add 0.5-1 mL of 5% K2CrO4 indicator into the flask and titrate to the
first permanent appearance of brick-red (reddish brown) Ag2CrO4. Read
the burette mark.
4. Repeat titration also two times. Calculate the median volumes of the
used AgNO3 solution.
5. Calculate the exact concentration of the Cl- solution.
Part II. Fajan’s method
Fajans’ method for the argentometric titration of chloride ion with silver
nitrate involved the use of fluorescein (HInd) as an adsorption indicator.

In an aqueous solution at pH 7, fluorescein will partially dissociate to form

negatively charged yellow-green fluoresceinate ions (Ind-).

Because this indicator is weakly basic, the indicator works best above pH 5.
However, the pH must be below about 9 to prevent precipitation of AgOH.
❖ In the early stages of a titration of chloride ion with silver nitrate, the colloidal
silver chloride particles formed are negatively charged because of the
adsorption of excess chloride ions onto the particles. The fluoresceinate ions,
which are negatively charged, are repelled by the negatively charged particles
and impart a yellow-green color to the solution.

❖ After the equivalence point, where the chloride ion concentration is very low,
the colloidal silver chloride particles strongly adsorb positively charged silver
ions, Ag+. Fluoresceinate ions are now attracted into the counter ion layer that
surrounds the particles and their color changes to pink.
Experimental Procedure
1. Load a burette with standard
0.05 M AgNO3 solution.

2. Pipet a 10.0 mL sample of the

unknown Cl- solution into a 100-
mL Erlenmeyer flask.
And point
3. Add 3-5 drops of 0.5% fluorescein indicator into the flask, and titrate to
the first permanent pink color of the adsorbed fluoresceinate ions
remains. Read the burette mark.

4. Repeat titration also two times. Calculate the median volumes of the
used AgNO3 solution.

5. Calculate the exact concentration of the Cl- solution.

Pre-Lab Calculations

1. A 0.0259g sample of Primary Standard grade NaCl was dissolved in 25 mL of

Water and titrated to its endpoint using an AgNO3 titrant. The starting burette
volume was 0.33 mL. The ending volume was 21.65 mL. Calculate the
concentration of the AgNO3 titrant.

2. A 0.0531g sample of an unknown powder was dissolved in 25 mL of Water

and titrated to its endpoint using the above titrant. The starting and endign
burette volumes were 0.15 mL and 32.05 mL respectively. Calculate the
percentage Chloride Ion in the sample.

3. 10.0456g of butter are analyzed using our procedure and the titrant above.
The burette volumes were 0.57 mL and 28.96 mL. Calculate the % NaCl of the
butter. Keep in mind the butter is extracted with 250 mL of Water and only 20
mL is titrated.
 Complexometric Titrations
• Part I. Standardization of EDTA solution

• Part II. Determination of total water hardness

• Part III. Determination of concentration of Ca2+(aq)

ions
Part I. Standardization of EDTA solution

Background
EDTA itself is a tetraprotic acid. H4Y is only sparingly soluble in water, so
the standard form of EDTA used analytically is usually the disodium salt
Na2H4Y. 2H2O (372.24 g/mol), which is much more soluble and available in
primary standard purity.

Structure of EDTA:
❖ In the complexometric titration method, a ligand (chelate) reacts
with the analyte (metal ions) to form a complex.

❖ EDTA (ethylenediaminetetraacteic acid) is an excellent chelating

agent. It forms very strong 1:1 complexes with almost every
divalent and trivalent metal ion depending on solution conditions.
Ignoring charges for the moment,

H2Y2- + M2+  MY2- + 2H+

❖ Although it is equilibrium, the reaction lies very far to the right. The
equilibrium formational constants, Kf, are on the order of 108- 1025
depending on the metal and other conditions.
• All cations are ordinary determined by EDTA titration after the sample has
been buffered to pH 9-10 (with ammonium buffer solution).

• In part II.1 of this experiment, an EDTA solution will be standardized

against the standard zinc sulphate solution. Once the exact concentration
of the EDTA solution is determined, the standard EDTA solution will be
used to find the total hardness, calcium and magnesium hardness in a
given water sample.

• Complexometric titration at pH about 9–10 using ETOO indicator gives

the concentration of EDTA
Experimental procedure

1. Load a burette with EDTA solution.

2. Pipet a 10.0 mL aliquot of standard

0.025M solution into 100-mL conical
flask.

3. Add 5-7 mL of ammonium buffer solution, and 3-5 drops of ETOO

indicator into the flask.

4. Titrate with EDTA solution until the solution just begins to change color
from wine-red to light sky blue. Read the burette mark.

5. Repeat titration also two times. Calculate the median volumes of the
used EDTA solution.

6. Calculate the exact concentration of the EDTA solution.

 Part II. Determination of total water hardness
Background
❖ EDTA forms complex with Ca2+ and Mg2+ ions in the solution.

❖ When Eriochrome Black T indicator (ETOO) is added to the solution at

pH around 9–10, it gives wine red colored unstable complex with Ca2+
and Mg2+ ions.

❖ When this wine red colored complex is titrated against EDTA solution,
the Ca2+ and Mg2+ ions forms stable metal complex with EDTA and
color changes from wine red to blue (color of ETOO indicator) at the
end point.

❖ Complexometric titration at pH about 9–10 using ETOO indicator gives

the concentration of EDTA or total amount of Ca2+ and Mg2+ ions in the
sample.
Experimental procedure

1. Load a burette with EDTA solution.

2. Pipet a 100.0 mL aliquot of water sample into 250-mL conical flask.

3. Add 5-7 mL of ammonium buffer solution NH4Cl/NH4OH, 3-5 drops of

ETOO (Eriochrome Black T) indicator into the flask.

4. Titrate with EDTA solution until the solution just begins to change
color from wine-red to light sky blue. Read the burette mark.

5. Repeat titration also two times. Calculate the median volumes of the
used EDTA solution.

6. Calculate the exact total hardness of water sample.

Part III. Determination of concentration of Ca2+(aq) ions

❖ After first determining the total water hardness, you will separately
determine the amounts of each of the two metal cations. You will titrate
samples to determine the concentration of Ca2+, only, by masking the
interference from Mg2+ by precipitating it from solution at a higher pH.
That is, you will add excess strong base to precipitate Mg2+ as insoluble
Mg(OH)2 and then titrate the remaining Ca2+ with EDTA using murexide
indicator.

Mg2+ + 2NaOH → Mg(OH)2(s) + 2Na+

❖ A separate titration using murexide as indicator at pH ~ 13 is applied to

determine calcium hardness. At the equivalence point, the solution
changes color from red to violet
Experimental procedure
1. Load a burette with EDTA solution.

2. Pipet a 100.0 mL aliquot of water sample into 250-mL conical flask.

3. Add 5-7 mL of 10% (w/w) NaOH solution, 3-5 drops of murexide

indicator into the flask.

4. Titrate with EDTA solution until the solution just begins to change
color from red to violet. Read the burette mark.

5. Repeat titration also two times. Calculate the median volumes of the
used EDTA solution.

6. Calculate the exact concentration of Ca2+(aq) ions, then calculate

the calcium and magnesium hardness of water sample.
 Spectrophotometric method
• Part I. Study the absorption spectrum of Fe (III)
and sulfosalicylic acid (UV-vis spectroscopy)

• Part II. Determination of iron

 Part I. Study the absorption spectrum of Fe (III) and
sulfosalicylic acid
Backgound
Properties
Chemical formula C7H6O6S
Molar mass 218.185 g/mol
Color: Colorless

Iron(III) chloride hexahydrate Iron(III) chloride solution

https://www.youtube.com/watch?v=wxrAELeXlek
https://www.youtube.com/watch?v=s5uIVQGFDE4
Chemical reaction:

Fe3+ + H2Sal ⇋ [Fe(Sal)]+ + 2H+ pH = 1-2,5 purple

Fe3+ + 2H2Sal ⇋ [Fe(Sal)2]- + 4H+ pH = 4-5 Red brown

Fe3+ + 3H2Sal ⇋ [Fe(Sal)3]3- + 6H+ pH = 9-10 Yellow

 Experimental procedure
❑ Survey complex absorption spectrum of Fe3+ in the different pH: pH 1.0
to 2.5, 4.0 to 5.0 and pH pH 9.0 to 10.0. Find their absorption maxima.

❑ Preparation 6 25.0 mL-flask type dispensing a liquid composition range

as the following table:

pH = 1-2,5 4.0-5.0 9.0-10.0

ml Flask F1 F2 F3 F4 F5 F6

Fe3+ 0.1 mg/ml 2.00 2.00 2.00

Sulfosalicylic acid 10% 2.50 2.50 2.50 2.50 2.50 2.50
CH3COOH+CH3COONa 5.00 5.00
NH4OH 10% 2.50 2.50
Distiilled water Dilute to the mark and mix well
Record the absorption spectrum of Fe(III) complex (a graph showing how A
varies with wavelength)

DR 3900
Spectrophotometer
UV-Vis 8453
Part II. Determination of iron
Background
❑ Absorbance is so important because it is directly proportional to
the concentration, C, of the light-absorbing species in the sample.
𝑷𝒐
Beer’s law: A = εbC = – logT = log (1-1)
𝑷

❑ Equation 1-1, which is the heart of spectrophotometry as applied to

analytical chemistry, is called the Beer-Lambert law, or simply
Beer’s law.

❑ Molar absorptivity is the characteristic of a substance that tells how

much light is absorbed at a particular wavelength. In our
experiment, if it applies to monochromatic radiation and the
pathlength, b can be fixed.

❑ Therefore, K = εb We have:

A = KC

❑ We can construct a calibration curve to determine K

 Constructing a calibration curve
❑ Constructing a calibration curve in pH = 9-10.

❑ Prepare four solutions from 0.50, 1.00, 1.50, and 2.00 mL of Fe

standard and prepare a blank containing no Fe as the following table.

❑ Graphs are critical to understanding quantitative relations. In our

experiment, we always want a graph to see if the calibration points lie
on a straight line. Find the slope K

❑ by the method of least squares.

F1 F2 F3 F4 F5
(blank*)
0.1 mg/ml Fe3+, mL 0.00 0.50 1.00 1.50 2.00
10%, sulfosalicylic acid, mL 2.50
10% NH4OH, mL 2.50
Distilled water Dilute to the mark and mix well
 Determination of unknown Fe (III)

❑ Pipet 2.00 mL of unknown Fe(III) into a 25-mL volumetric flask, add

2.5 mL of sulfosalicylic acid, mix well.

❑ Add 2.5 mL of 10% NH4OH, then dilute the solution with distilled
water to the mark and mix well

❑ Measure the absorbance of the unknown Fe(III) solution at 424 nm.

❑ Using the calibration curve (or its least-squares parameters), find the
number of milligrams/mL of the unknown Fe(III).
Acid – base titration by using a pH electrode
Background of experiment
❑ A pH electrode to follow the course of an acid-base titration.

❑ The pH changes slowly during most of the reaction and rapidly near
the equivalence point.

❑ The first and second derivatives of the titration curve to locate the end
point.

❑ From the mass of unknown acid or base and the moles of titrant, we
can calculate the molecular mass of the unknown.

Chemical reaction: HCl + NaOH = NaCl + H2O

❑ A typical pH combination electrode, incorporating both glass and

reference electrodes in one body. A line diagram of this cell can be
written as follows:
❑ The pH-sensitive part of the electrode is the thin glass bulb or cone at
the bottom of the electrodes in Figures 2-1 and 2-2. The reference
electrode at the left of the preceding line diagram is the coiled Ag│AgCl
electrode in the combination electrode in Figure 2-1. The reference
electrode at the right side of the line diagram is the straight Ag│AgCl
electrode at the electric potential difference across the glass
membrane. The salt bridge in the line diagram is the porous plug at the
bottom-right side of the combination electrode in Figure 2-1.
❑ The response of real glass electrodes is described by the Nernst-like
equation:
E = constant + 0.05916 log 𝒂𝑯+(𝒐𝒖𝒕𝒔𝒊𝒅𝒆)
E = constant – 0.05916 pH (at 25°C)
Experimental Procedure

❑ 100-mL beaker: 10.00 mL of HCl, add 30-40

mL of distilled water.

❑ Burette: 0.1000M standard solution NaOH

❑ Rinse the electrodes well with distilled water

and blot them dry with a tissue before
immersing in any new solution.

❑ Assemble the glass combination electrode

as the diagram (Figure 2-1) Figure 2-1. Diagram of a glass
combination electrode with a
silver-silver chloride reference
electrode
 Figure 2-2 (a) Glass-body combination electrode with pH-sensitive glass bulb at
the bottom. The porous ceramic plug (the salt bridge) connects analyte solution to
the reference electrode. Two silver wires coated with AgCl are visible inside the
electrode. (b) A pH electrode with a platinum diaphragm (a bundle of Pt wires),
which is said to be less prone to clogging than a ceramic plug.
1. The rough titration
The first titration is intended to be rough, so that you will know the
approximate end point in the next titration. Allow the electrode to
equilibrate for 1 min with stirring and record the voltage. For the rough
titration, add 1 mL of titrant at a time so that you can estimate the
equivalence volume to within 1 mL, record the voltage. Near the end
point, there is a jump voltage.

2. The careful titration

Add 1 mL of titrant at a time, record the voltage. Near the end point, add
0.1 or 0.2 mL of titrant, record the voltage. After the equivalence volume,
continue with 1 mL increments, record five more points. The equivalence
point has the most rapid change in voltage.
Data analysis
- Construct a graph of E versus titrant volume from the careful data

- Construct a graph of the first derivative ΔE/ΔV versus titrant

volume from the careful data
Electrogravimetry method for determination of copper
Background
❑ In electrogravimetric analysis, analyte is quantitatively deposited on
an electrode by electrolysis. The electrode is weighed before and
after deposition. The increase in mass tells us how much analyte
was deposited. We can measure in a solution by reducing it to Cu(s)
on a clean Pt gauze cathode with a large surface area (Figure 3-1).
O2 is liberated at the counter electrode.

❑ Suppose we dip Cu and Pt electrodes into a solution and force

electric current through to deposit copper metal at the cathode and
to liberate O2 at the anode.
❑ In electrolysis, electrons come from the negative terminal of the power
supply into the cathode of the electrolysis cell. E(cathode) is the
potential of the electrode connected to the negative terminal of the
power supply and E(anode) is the potential of the electrode connected
to the positive terminal.

❑ If the net reaction contains 0.2M Cu2+ and 1.0M H+ and liberates O2 at a
pressure of 1.0 bar, we find

Ecell = – ENernst = – (E+ – E-) = – (Eanode – Ecathode) = Ecathode – Eanode

0.05916 1/2 0.05916

= − 𝐸1𝑜𝑂 +2𝐻 + /𝐻 𝑂
+ 𝑙𝑜𝑔𝑃𝑂 [𝐻 + ]2 𝑜
+ 𝐸𝐶𝑢 2+ /𝐶𝑢 + log[𝐶𝑢 2+ ]
2 2 2 2 2 2

0.05916
= – 1,229 + (0,337+ log0.200) = – 0,913V
2
Figure 3-1. (a) Electrogravimetric analysis. Analyte is deposited on the large Pt gauze electrode. If
analyte is to be oxidized, rather than reduced, the polarity of the power supply is reversed so that
deposition still occurs on the large electrode. (b) Outer Pt gauze electrode.
This is the voltage that would be read on the potentiometer in Figure 3-1
if there were negligible current. The voltage is negative because the
positive terminal of the potentiometer is connected to the negative side
of the power supply. The free energy change computed in the margin is
positive because the reaction is not spontaneous. We need the power
supply to force the reaction to occur. If current is not negligible,
overpotential, ohmic potential, and concentration polarization can
change the voltage required to drive the reaction.

In our experiment, the applied voltage is 1.8-2.0V.

Experimental Procedure
Prepare the gause cathode
❑ Handle the Pt gauze cathode with a tissue, touching only the thick stem,
not the wire gauze.
❑ Immerse the electrode in hot 8 M HNO3 to remove previous deposits, rinse
with water and dry at 105˚C for 5 min, cool for 5 min, and weigh
accurately.
❑ If the electrode contains any grease, it can be heated to red heat over a
burner after the treatment above.
Prepare solution for the electrogravimetric
❑ Pipet 2.00 mL of unknown into a 250-mL beaker containing a magnetic
stirring bar
❑ Add about 5 mL of 6N H2SO4 6N and 5 ml of 6N HNO3
❑ Add distilled water up to 150 mL
Electrogravimetric
Position the cathode so that the top 5 mm are above the liquid level after
magnetic stirring is begun. Adjust the voltage to 2 V.
How do you know when electrolysis is complete?

• The first method: When the blue color of Cu(II) has disappeared, add
some distilled water so that new Pt surface is exposed to the
solution. If no further deposition of Cu occurs on the fresh surface
in 15 min, the electrolysis is complete. If deposition is observed,
continue electrolysis and test the reaction for completeness again.

• The second method: Remove a drop of solution and perform a

qualitative test for analyte:

Chemical reaction: K4[Fe(CN)6] + 2 Cu2+ → Cu2[Fe(CN)6]↓ + 4 K+

potassium ferrocyanide Brownly red

• If the brownly red color is observed, continue to electrolysis, and

test the reaction for the completeness again. If there is no
precipitate, the electrolysis is done.
❑ Without turning off the power, lower the voltage to 1V, higher the
electrode, remove the beaker, and wash the electrode with a beaker
of distilled water.

❑ Then the current can be turned off. (If current is disconnected

before removing the cathode from the liquid and rinsing off the acid,
some Cu could redissolve.)

❑ Wash the cathode gently with water, dry at 105˚C for 5 min, cool in a
desiccator for 5 min, and weigh.
 Determination of pesticide residues by gas
chromatography -mass spectrometry (GC-MS)

The objective of this experiment is to determine a pesticide residue, which is an

organic chlorine pesticide: 1-chloro-4- [2,2-dichloro-1- (4 -chlorophenyl) ethyl]
benzene, abbreviated as p,p'-DDD, in vegetables by gas chromatography -
mass spectrometry
https://www.youtube.com/watch?v=PV4NYBUaUrQ
https://www.youtube.com/watch?v=OVXCcBw0iCQ
IV. EXPERIMENTAL
4.1.Prepare the standard working solutions
4.2.Prepare the sample
4.3.Mass spectrum of DDD
4.3.1. Analytical conditions by GC-MS.
4.3.2. Calibration curve and DDD determination
- The calibration curve is established based on the peak area of the analyte and
their concentrations (vials 1-5). The intercept should be close to 0 and the linear
regression correlation coefficient (R2) should be greater than 0,995.
- The standard and test samples are analyzed under the conditions as shown in
Table 2 and Table 3 in SIM mode