VIETNAM NATIONAL UNIVERSITY – HO CHI MINH CITY

HO CHI MINH CITY UNIVERSITY OF TECHNOLOGY

DEPARTMENT OF CHEMICAL ENGINEERING

DETERMINATION OF Ca2+, Mg2+ AND Fe2+

IN WATER
SUBJECT: ANALYTICAL CHEMISTRY
GROUP 10_CH2113_ CC01

INSTRUCTOR: DR. TRAN THI KIEU ANH

AUTHOR: LE VU PHUONG NHU – 25% – 2052202

LIEU MANH HUNG – 25% – 2053070
NGUYEN MINH HOANG YEN – 25% – 2052335
NGUYEN MINH TRI – 25% – 2053532

HO CHI MINH CITY, 24th NOVEMBER, 2021

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1. INTRODUCTION
The safety of drinking water is a very important public health issue. The
World Health Organization have established well-defined standards for drinking
water purity. Nowadays, almost the water source is mixed with ionic impurities
that we called water hardness. Water ‘hardness’ is a measure of the amount of
hard water cations in water. These hard water cations include calcium,
magnesium, iron, zinc and the other polyvalent metal ions. In most water
samples, calcium and magnesium are the chief contributors to water hardness. It
is unfit for drinking, bathing, washing and it also forms scales in boilers. Hence
it is necessary to estimate the amount of hardness producing substances present
in the water sample. Once it is estimated, the amount of chemicals required for
the treatment of water can be calculated. In this report we will discuss about the
2+¿ ¿

content of Ca2+¿ , Mg in water by gravimetric method of analysis, titrimetric

2+¿∧Fe ¿
¿

method of analysis and spectroscopic method of analysis.

2. THEORY
2.1 Gravimetric methods of analysis
2.1.1 Principle
Gravimetric methods are quantitative methods based on measurement of
weight of an analyte or a compound containing the analyte.
Types of analysis:
 Precipitation
 Electrogravimetry
 Volatilization gravimetry (indirect method)
 Particulate gravimetry (direct method)
 In this report, we only focus on Precipitation Gravimetry as the
application for determination of Ca2+ and Mg2+.
2.1.2 Precipitation Gravimetry
Gravimetry is among the most accurate and precise methods of
macroquantitative analysis.
The analyte is selectively converted to an insoluble form.
The separated precipitate is dried or ignited, possibly to another form, and
is accurately weighed.

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The weight of analyte in the desired form is calculated from the weight of
the precipitate and a knowlegde of its chemical composition (stoichiometric
mole relationships).
The steps required for Precipitation Gravimetry:
 Preparation of the solution: This involves several steps
including adjustment of the pH of the solution in order for the precipitate
to occur quantitatively and get a precipitate of desired properties,
removing interferences, adjusting the volume of the sample to suit the
amount of precipitating agent to be added.
 Precipitation:
- This requires addition of a precipitating agent solution to the
sample solution. Upon addition of the first drops of the precipitating
agent, supersaturation occurs, then nucleation starts to occur where every
few molecules of precipitate aggregate together forming a nucleus. At this
point, addition of extra precipitating agent will either form new nuclei or
will build up on existing nuclei to give a precipitate. Relative
Q–S
supersaturation ¿ S .
- The Q is the concentration of reactants before precipitation, S
is the solubility of precipitate in the medium from which it is being
precipitated. Therefore, to get particle growth instead of further nucleation
we must make the relative supersaturation ratio as small as possible. The
optimum conditions for precipitation which make the supersaturation low
are:
+ Precipitation using dilute solutions to decrease Q
+ Slow addition of precipitating agent to keep Q as low as possible
+ Stirring the solution during addition of precipitating agent to avoid
concentration sites and keep Q low
+ Increase solubility by precipitation from hot solution
+ Adjust the pH to increase S, but not too much increase np as we do
not want to lose precipitate by dissolution
+ Usually add a little excess of the precipitating agent for quantitative
precipitation and check for completeness of the precipitation
 Digestion of the precipitate: The precipitate is left hot (below
boiling) for 30 min to one hour for the particles to be digested. Digestion
involves dissolution of small particles and reprecipitation on larger ones
resulting in particle growth and better precipitate characteristics. This
process is called Ostwald ripening. An important advantage of digestion is

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observed for colloidal precipitates where large amounts of adsorbed ions

cover the huge area of the precipitate. Digestion forces the small colloidal
particles to agglomerate which decreases their surface area and thus
adsorption. You should know that adsorption is a major problem in
gravimetry in case of colloidal precipitate since a precipitate tends to
adsorb its own ions present in excess, Therefore, forming what is called a
primary ion layer which attracts ions from solution forming a secondary
or counter ion layer. Individual particles repel each other keeping the
colloidal properties of the precipitate. Particle coagulation can be forced
by either digestion or addition of a high concentration of a diverse ions
strong electrolytic solution in order to shield the charges on colloidal
particles and force agglomeration. Usually, coagulated particles return to
the colloidal state if washed with water, a process called peptization.
 Washing and Filtering the precipitate: It is crucial to wash the
precipitate thoroughly to remove all adsorbed species that would add to
the weight of the precipitate. One should be careful to use too much water
since part of the precipitate may be lost. Also, in case of colloidal
precipitates we should not use water as a washing solution since
peptization would occur. In such situations dilute nitric acid, ammonium
nitrate, or dilute acetic acid may be used. Usually, it is a good practice to
check for the presence of precipitating agent in the filtrate of the final
washing solution. The presence of precipitating agent means that extra
washing is required. Filtration should be done in appropriately sized
ignition filter paper.
 Drying and Ignition: The purpose of drying (heating at about
120 - 150 ℃ in an oven) or ignition in a muffle furnace at temperatures
ranging from 600 - 1200 ℃ is to get a material with exactly known
chemical structure so that the amount of analyte can be accurately
determined.
 Precipitation from Homogeneous Solution: To make Q
minimum we can, in some situations, generate the precipitating agent in
the precipitation medium rather than adding it. For example, to precipitate
iron as the hydroxide, we dissolve urea in the sample. Heating of the
solution generates hydroxide ions from the hydrolysis of urea. Hydroxide
ions are generated at all points in solution and thus there are no sites of
concentration. We can also adjust the rate of urea hydrolysis and thus
control the hydroxide generation rate. This type of procedure can be very
advantageous in case of colloidal precipitates. The identification of the
quantity of an unknown solute in a solution by making it the limiting

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reagent of precipitation reaction, weighting the mass of the resulting

precipitate and then using the stoichiometry of the precipitation reaction
to determine the moles of the unknown. This technique takes advantage of
the solubility rules, and the strategy is to use a double displacement
reaction where where one of the products is soluble, while the other forms
a precipitate.
2.1.3 Calculation of results - Precipitation Gravimetry
- Solid sample:
100
%X =m' × F ×
m

- Solid sample (dilution):

V 100
%X =m' × F × ×
v m

- Liquid sample:
V 1000
X (g /l)=m' × F × ×
v1 v

{
m ( g ) :mass of sample
'
m ( g ) :mass of the compound weighed
M ( formulaweight of analyte)
F= ×k
M ( formulaweight of compound weighed )

2.2 Titrimetric methods of analysis

2.2.1 Principle
Titrimetric methods include a large and powerful group of quantitative
procedures based on measuring the amount of a reagent of known concentration
that is consumed by an analyte.
Titrimetric methods are classified into four groups based on the type of
reaction involved. These groups are acid–base titrations, in which an acidic or
basic titrant reacts with an analyte that is a base or an acid; complexometric
titrations involving a metal–ligand complexation reaction; redox titrations,
where the titrant is an oxidizing or reducing agent; and precipitation titrations,
in which the analyte and titrant react to form a precipitate.
 In this report, we only focus on Complexometric Titrations as the
application for determination of Ca2+ and Mg2+.

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2.2.2 Complexometric Titration

Complexation titration is a titration in which the reaction between the
analyte and titrant is a complexation reaction.
The most widely used of new ligands was ethylenediaminetetraacetic acid,
EDTA, which forms strong 1:1 complexes with many metal ions. The first use
of EDTA as a titrant occurred in 1946, when Schwarzenbach introduced
metallochromic dyes as visual indicators for signaling the end point of a
complexation titration.

Figure 1. Structure of EDTA

The equivalence point of a complexation titration occurs when
stoichiometrically equivalent amounts of analyte and titrant have reacted. For
titrations involving metal ions and EDTA, the equivalence point occurs when
CM and CEDTA are equal and may be located visually by looking for the titration
curve’s inflection point.
As with acid–base titrations, the equivalence point of a complexation
titration is estimated by an experimental end point. A variety of methods have
been used to find the end point, including visual indicators and sensors that
respond to a change in the solution conditions. For determining water hardness,
finding the end point with a visual indicator is chosen as the method used.
Finding the End Point with a Visual Indicator: Most indicators for
complexation titrations are organic dyes that form stable complexes with metal
ions. To function as an indicator for an EDTA titration, the metal–indicator
complex must possess a color different from that of the uncomplexed indicator.
Furthermore, the formation constant for the metal–indicator complex must be
less favorable than that for the metal–EDTA complex. The indicator, Inm–, is
added to the solution of analyte, forming a colored metal–indicator complex,
MInn-m. As EDTA is added, it reacts first with the free analyte, and then

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displaces the analyte from the metal–indicator complex, affecting a change in

the solution’s color.
2.2.3 Calculation of results
- Liquid sample:
−3 V 1 1000
X ( g/l )=C C × 10 ×V C ×equivalent X × ×
VX V

- Solid sample:
−3 V 1 100
%X =CC ×10 × V C × equivalent X × ×
VX m

{
C c :normality
C ( standard ) :the standard solution with knownconcentration
X ( analyte ) :the solution X with known concentration

2.3 Spectroscopic methods of analysis

2.3.1 Principle
Colorimetric analysis is based on the change in the intensity of the color of
a solution with variations in concentration. Colorimetric methods represent the
simplest form of absorption analysis. The human eye is used to compare the
color of the sample solution with a set of standards until a match is found.
Radiation is a form of energy and we are constantly reminded of its
presence via our sense of sight and ability to feel radiant heat. It may be
considered in terms of a wave motion where the wavelength, λ, is the distance
between two successive peaks. The frequency, ν, is the number of peaks passing
a given point per second. These terms are related so that:
c =νλ
where c is the velocity of light in a vacuum. The full electromagnetic
radiation spectrum is continuous and each region merges slowly into the next.
For spectroscopy purposes, we choose to characterize light in the ultraviolet and
visible regions in terms of wavelength expressed in nanometers. Other units
which may be encountered, but whose use is now discouraged, are the Angstrom
(Å) and the millimicron (mµ).
The energy of a photon absorbed or emitted during a transition from one
molecular energy level to another is given by the equation
E=hν= hc/λ

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h :Planck's constant
ν: frequency of the photon.

Figure 2. Electromagnetic Spectrum- Regions

An increase in sensitivity and accuracy results when a spectrophotometer is
used to measure the color intensity. Basically, it measures the fraction of an
incident beam of light which is transmitted by a sample at a particular
wavelength. You will use a Spectronic 21 in this experiment. There are two
ways to measure the difference in intensity of the light beam. One is the percent
transmittance, %T, which is defined as:

For any given compound, the amount of light absorbed depends upon (a)
the concentration, (b) the path length, (c) the wavelength and (d) the solvent.
Absorbance is related to the concentration according to the Beer-Lambert law:

where ε is molar absorptivity ( M −1 c m−1 ), b is the path

length (cm) and c is the concentration (mol/L ).
2.3.2 Instrument

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Figure 3. Some kinds of Spectrophotometer

2.3.3 Performing a quantitative measurement:
Step 1: Prepare a quantitative sample on an analytical or semi-analytical
balance then dilute it with suitable solvent.
Step 2: Turn on the UV-Vis spectrometer and allow the lamps to warm up
for an appropriate period of time (around 20 min) to stabilize them.
Step 3: Fill a cuvette with the solvent for the sample and make sure the
outside is clean. This will serve as a blank and help account for light losses due
to scattering or absorption by the solvent.
Step 4: Place the cuvette in the spectrometer. Make sure to align the
cuvette properly, as often the cuvette has two sides, which are meant for
handling (may be grooved) and are not meant to shine light through.
Step 5: Take a reading for the blank. The absorbance should be minimal,
but any absorbance should be subtracted out from future samples. Some
instruments might store the blank data and perform the subtraction
automatically.
3. RESULT
2+ ¿¿

3.1 Determination of Ca2+¿∧Mg ¿

in water by gravimetric method of analysis
Standard criteria:
Water hardness is calculated as the sum of Ca 2+ and Mg2+ content. If the
hardness does not exceed 300 mg/l, it can be used for normal activities.
TDS or Total Dissolved Solids means concentration of dissolved particles
or solids in water. TDS for drinking water should be less than 300mg/liter and
the maximum limit considered safe is 500mg/liter – this is ideal for healthy
mineral-rich water.

Figure 4. TDS range for water

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Type of gravimetric methods: Precipitation gravimetry

 Ca2+:
Implementation process:
Step 1: Preparation of solution
An excess of oxalic acid, H2C2O4, is added to a measured, known volume
of water.
Step 2: Precipitation
By adding a reagent, here ammonium oxalate¿ ¿, the calcium will
precipitate as calcium oxalate (CaC 2O4). The proper reagent, when added to
aqueous solution, will produce highly insoluble precipitates from the positive
and negative ions that would otherwise be soluble with their counterparts
The reaction is:
Formation of calcium oxalate: Ca2+(aq) + C2O42- (aq) → CaC2O4 (s)
Step 3: Washing-Drying-Igniting
The precipitate is collected, dried and ignited to high (red) heat which
converts it entirely to calcium oxide (CaO).
The reaction is pure calcium oxide formed:
CaC2O4 (s) → CaO(s) + CO(g)+ CO2(g)
Step 4: Weighing
The pure precipitate is cooled, then measured by weighing, and the
difference in weights before and after reveals the mass of analyte lost, in this
case calcium oxide (CaO).
Calculation: Assume we prepare 100ml of water sample
Assume we meassure the weigh of CaO is 2.268mg = 2.268×10−3g
m CaO 2.268 × 10−3 −5
We have nCaO = M CaO
=
56
=4.05 ×10 (mol)

nC a 2 +¿
=n CaC ¿nCaO=4.05 × 10−5(mol)¿
2 O4

C nC a 2+¿
4.05 × 10
−5
=4.05 ×10 ( M ) =4.05 ×10 ( mol/l ) ¿¿
−4 −4
M Ca =
2+¿ =
V water sample 100× 1 0−3
CM × M CaCO × 1 03 4.05× 10−4 ×100 × 10 3
Water hadness(C a2+¿¿ = Ca 2+ ¿ 3
= =40.5 ppm ¿
1 1
 Mg : 2+

Implementation process:
Step 1: Preparation of solution
An excess of acid phosphoric, H3PO4, is added to a measured, known
volume of water.
Step 2: Precipitation
By adding a reagent, here diamoni hydro phosphat ¿ ¿, the magnesium will
precipitate as ammonium magnesium phosphate ¿ ¿). The proper reagent, when

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added to aqueous solution, will produce highly insoluble precipitates from the
positive and negative ions that would otherwise be soluble with their
counterparts
¿¿
Step 3: Washing-Drying-Igniting
The precipitate is collected, dried and ignited to high heat which converts it
entirely to magnesium pyrophosphate (Mg ¿ ¿ 2 P2 O7) ¿
The reaction is pure magnesium pyrophosphate formed:
2 MgN H 4 P O4 → Mg 2 P2 O7 + 2 N H 3 + H 2 O
Step 4: Weighing
The pure precipitate is cooled, then measured by weighing, and the
difference in weights before and after reveals the mass of analyte lost, in this
case magnesium pyrophosphate ( Mg ¿ ¿ 2 P2 O7) . ¿
Calculation: Assume we prepare 100ml of water sample
Assume we meassure the weigh of Mg 2 P2 O7 is 5.55mg = 5.55×10−3g
mMg P O 5.55× 10 −5
−3

We have n Mg P O = M 2 2 7
2 2 7
=
222
=2.5 ×1 0 (mol)
Mg2 P2 O7
n Mg 2+ ¿
=n MgN H PO =2n Mg P O =2 ׿ 2.5 ×1 0−5 =5× 1 0−5 (mol)
4 4 2 2 7

C n Mg2+¿
5 ×10
−5
=5 × 10 ( M ) =5 ×10 ( mol/ l ) ¿¿
−4 −4
M Mg = 2+¿ =
V water sample 100 ×1 0−3

5 ×10 ×100 ×1 0 CM × M CaC O ×103

−4 3
Water hadness ( Mg 2+¿¿ = = =50 ppm¿ Mg 2+¿ 3

1 1
Total water hardness ¿Water hadness (C a2+¿¿ +Water hadness¿
¿ 40.5+50=90.5 ppmCaC O3
⟹ We can use this water for for normal activities.
3.2 Determination of Ca2+¿∧Mg in water by titrimetric method of analysis
2+ ¿¿
¿

Type of titrimetric methods: Complexometric Titration

Implementation process:
The ions involved in water hardness, i.e. Ca2+¿ ¿ (aq) and Mg 2+¿¿ (aq), can be
determined by titration with a chelating agent, ethylenediaminetetraacetic acid
(EDTA), usually in the form of disodium salt ( H 2 Y 2−¿ ¿). The titration reaction is:

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Eriochrome Black T is commonly used as indicator for the above titration.

At pH=10, Ca2+¿ ¿ (aq), Mg 2+¿¿ (aq) ion first complex with the indicator as CaIn+¿¿
(aq) and MgIn +¿¿(aq) which are wine red. As the stronger ligand EDTA is added,
the CaIn+¿¿ (aq) complex and MgIn +¿¿(aq) are replaced by the CaY 2−¿¿(aq) complex
which are blue. The end point of titration is indicated by a sharp colour change
from wine red to blue. Titration using Eriochrome Black T as indicator
determines total hardness due to Ca2+¿ ¿ (aq) and Mg 2+¿¿(aq) ions.

Hardness due to Ca2+¿ ¿ (aq) ion is determined by a separate titration at a

higher pH, by adding NaOH solution to precipitate Mg ¿, using Fluorexone as
indicator. At pH=12.5, Ca 2+¿ ¿ (aq) first complexes with the indicator as CaIn+¿¿
(aq) which is orange. As the stronger ligand EDTA is added, the CaIn+¿¿ (aq)
complex is replaced by the CaY 2−¿¿(aq) complex which is red at the end point.

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Calculation
Assume we have 100mL water sample and at pH=10, we need
V EDTA =5.05 mL with EDTA 0,01M for both Ca 2+¿ ¿ (aq) and Mg 2+¿¿ (aq) titration. At
pH=12.5, we need V EDTA =2.05 mL with EDTA 0,01M for Ca 2+¿ ¿ (aq) titration.
At pH=12.5
Water hardness (Ca2+¿ ¿ (aq))(ppm CaC O3 ¿=¿ ¿
( 2.05× 10−3 ×0.01 ) ×100 ×10 3
¿ =20.5 ( mg /l )=20.5(ppm )
100 ×10−3

Water hardness ( Mg 2+¿¿ (aq))(ppm CaC O3 ¿=¿ ¿

((5.05−2.05)×10−3 × 0.01 ) ×100 ×103
¿ =30 ( mg/l )=30( ppm)
100× 10−3
→ Total water hardness (ppm CaC O3)= Water hardness (Ca 2+¿ ¿ (aq))(ppm
CaC O3 ¿+ ¿ Water hardness ( Mg 2+¿¿ (aq))(ppm
CaC O3 ¿=20.5 [ ppm ] +30 [ ppm ] =55.5( ppm)

→This is slightly hard water (50−150 ppm . Basing on the standard criteria for
using water to drink (must be less than 300ppm), this water can be used for
drinking but actually if water hardness is higher than 50ppm in cooking
equipments they can have white precipitation.
3.3 Determination of Fe2+ ¿¿ in water by spectroscopic method of analysis
Standard criteria:
Due to the standard of clean water QCVN 01 2009/BYT, If the
concentration of Fe in the water does not exceed 0.3 mg/l, it can be used for
drinking and normal activities.

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Type of spectroscopic methods: Quantitative analysis: A spectroscopic

method in which the concentration of Fe2+ ¿¿in water is determined by using the
linear standard curve.
Implementation process:
1,10-phenantroline or or-phenantroline is a heterocyclic organic compound,
which forms strong complexes with many metal ions

Figure 5. Structure of 1,10-phenantroline

Iron in the +2 oxidation state reacts with o-phenanthroline to form the
orange-red Fe(o-phen)32+ complex.

Due to a
faster rate of
complex

formation in more acidic solutions, the reaction is usually carried out within the
pH range of 3.0–3.5. Any iron present in the +3 oxidation state is reduced with
hydroxylamine before adding o-phenanthroline. The most important interferents
are strong oxidizing agents; polyphosphates; and metal ions, such as Cu 2+, Zn2+,
Ni2+, and Cd2+. Interferences from oxidizing agents are minimized by adding an
excess of hydroxylamine, whereas the interference from polyphosphate is
minimized by boiling the sample in the presence of acid. Absorbances of
standard and sample solutions are measured at 510 nm (pathlength b = 1cm).
We prepare 100ml sample of water then take 10ml of sample to perform
complex reaction in 100.0 mL–volumetric flask. . Standard solutions are
prepared from a stock solution of 1.00 M x 10-3 M Fe3+ in 50.0 mL–volumetric
flasks. Absorbances of sample and standard solutions are reported in the table
below:

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Samples
C0 C1 C2 C3 C4 C5 M0 M1

V(0.00100 M Fe2+ ¿¿, ml 0 1.00 2.00 3.00 4.00 5.00

C ( Fe3 +¿¿ , mol /L
A 0 0.22 0.432 0.653 0.875 1.092 0.003 0.443
1
Calculation:
Base on the information provided in the table above, we can make the
linear standard curve:
1.2

f(x) = 0.218371428571429 x − 0.000428571428571445

1

0.8

0.6

0.4

0.2

0
0 1 2 3 4 5 6

So we have the equation of the curve: A=0.2184C-0.0004

( A1 −A 0 )+ 0.0004 (0.443−0.003)+ 0.004
M 1= = =2.033 ppm >0.3 ppm
0.2184 0.2184

 This sample of water is not considered to be clean enough to be used due

to the standard of clean water QCVN 01 2009/BYT.

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