I.

Experiment Title : Complexometry and Its Application

II. Experiment Date : December 19th, 2014 At 07.00
III. End of the Experiment : December 19th, 2014 At 11.30
IV. Experiment Purpose : 1. Making and determining(standardization) of Na-
EDTA solution
2. Determine the hardness of water Of PDAM water

V. Basic Theory
A. Complexometry

Complexometric titration (sometimes chelatometry) is a form of volumetric

analysis in which the formation of a colored complex is used to indicate the end point
of a titration. Complexometric titrations are particularly useful for the determination
of a mixture of different metal ions in solution. An indicator capable of producing an
unambiguous color change is usually used to detect the end-point of the titration.
A complex is a molecule or ion for-
med by the reaction of two or more ions or
molecules capable of independent exis-
tence. The most important complexation
reactions from an analytical point of view
are those between a metal ion in solution and
a complexing agent. A metal atom can usu-
ally form a bond with one or more donor
atoms which have at least one unshared pair
of electrons. The number of donor atoms which bond with a given atom depends on
the number of electron pairs that the metal ion can accept, in other words, the
coordination number of the metal ion. Complexing agents, or ligands, which can
provide more than one pair of electrons (multidentate ligands), are also called
chelating agents.
Complexometric titrations are particularly useful for determination of a mixture
of different metal ions in solution. An indicator with a marked color change is usually
used to detect the end-point of the titration.
In a complexometric titration, a solution containing the free metal ion of interest
is titrated with a solution of chelating agent until all of the metal ions are completely

Group IV|Complexometry and Its Application 1

complexed. The endpoint is usually measured with an indicator ligand that forms a
colored complex with the free metal ion.
Chelating Agent: EDTA

The most important chelating agent in analytical chemistry is ethelyenedia-

minetetraacetic acid (EDTA). The tetrabasic form of this acid forms complexes
with virtually all metal ions. EDTA is a hexadentate ligand; each of the acid oxy-
gens and each of the amine nitrogens can donate one electron pair. The metal ion
is usually held in a one-to-one complex with EDTA. The complexes have four or
five membered rings, contributing significantly to their stability. Unfortunately,
EDTA cannot be easily used as a primary standard. It is available in pure form,
but must be dried at 80°C for several days to obtain the precise composition of
the dihydrate. In any case, standardization of EDTA titrant against a solution of
the metal ion to be determined helps to eliminate any errors in endpoint selection.

pKa-2 = 0.0
pKa-1 = 1.5
pKa1 = 2.0
pKa2 = 2.66
pKa3 = 6.16
pKa4 = 10.24

It is important to realize that the electron pairs of the carboxylic acid groups
of EDTA are only available to the metal ion when the acid is dissociated. This
means that the effectiveness of the complexing agent is strongly affected by pH.
At low pH EDTA will be in the acid form and will not be an effective complexing
agent. Additionally, many metal ions form complexes with hydroxide ions.
Hydroxide ions compete with the chelating agent for coordination sites in the me-
tal ion. Therefore, the effectiveness of the complexing agent will also be reduced
at high pH. For a given chelating agent and metal ion, there will be an optimum
pH for the titration which will depend on the pK a values for the chelating agent
and the formation constants for the metal-hydroxide complexes.

Group IV|Complexometry and Its Application 2

 Complex Titration with EDTA

EDTA, ethylenediaminetetraacetic acid, has four carboxyl groups and two

amine groups that can act as electron pair donors, or Lewis bases. The ability of
EDTA to potentially donate its six lone pairs of electrons for the formation of co-
ordinate covalent bonds to metal cations makes EDTA a hexadentate ligand.
However, in practice EDTA is usually only partially ionized, and thus forms fe-
wer than six coordinate covalent bonds with metal cations.

Disodium EDTA is commonly used to standardize aqueous solutions of

transition metal cations. Disodium EDTA (often written as Na2H2Y) only forms
four coordinate covalent bonds to metal cations at pH values ≤ 12. In this pH
range, the amine groups remain protonated and thus unable to donate electrons to
the formation of coordinate covalent bonds. Note that the shorthand form Na4-
xHxY can be used to represent any species of EDTA, with x designating the
number of acidic protons bonded to the EDTA molecule.

EDTA forms an octahedral complex with most 2+ metal cations, M 2+, in

aqueous solution. The main reason that EDTA is used so extensively in the
standardization of metal cation solutions is that the formation constant for most
metal cation-EDTA complexes is very high, meaning that the equilibrium for the
reaction:
M2+ + H4Y → MH2Y + 2H+
lies far to the right. Carrying out the reaction in a basic buffer solution removes
H+ as it is formed, which also favors the formation of the EDTA-metal cation
complex reaction product. For most purposes it can be considered that the for-
mation of the metal cation-EDTA complex goes to completion, and this is chiefly
why EDTA is used in titrations / standardizations of this type.

The equilibrium involved in EDTA titration:

1. The stability of complex formed: The greater the stability constant for complex
formed, larger the charge in free metal concentration (pM) at equivalent point
and more clear would be the end point.

Group IV|Complexometry and Its Application 3

2. The number of steps involved in complex formation: Fewer the number of
steps required in the formation of complex, greater would be the break in
titration curve at equivalent point and clear would be the end point.
3. Effect of pH: During a complexometric titration, the pH must be constant by
use of a buffer solution. Control of pH is important since the H+ ion plays an
important role in chelation. Most ligands are basic and bind to H+ ions
throughout a wide range of pH. Some of these H+ ions are frequently
displaced from the ligands (chelating agents) by the metal during chelate
formation.

Indicators

To carry out metal cation titrations using EDTA, it is almost always neces-
sary to use a complexometric indicator to determine when the end point has been
reached. Common indicators are organic dyes such as Fast Sulphon Black, Erio-
chrome Black T, Eriochrome Red B, Patton Reeder, or Murexide. Color change
shows that the indicator has been displaced (usually by EDTA) from the metal
cations in solution when the end point has been reached. Thus, the free indicator
(rather than the metal complex) serves as the endpoint indicator.

EBT indicators
The structure of Eriochrome Black T are shown below

OH OH
-
O3S N N

NO2
EBT is blue in a buffered solution at
pH 10. It turns red when Ca2+ ions (Underwood, 1998)

Chelate metal formed with Eriochrome Black T molecule with the disappe-
arance of hydrogen ions from phenolate –OH and formation bonding bet-
ween metal ion and oxygen atoms and also azo-group. This indicator
forming red wine stable complex 1:1 with some cations, such as Mg 2+, Ca2+,

Group IV|Complexometry and Its Application 4

Zn2+, and Ni2+. Most of the EDTA titration occur in buffer pH 8-10, a range
where the dominant form of EBT is HIn2- blue colored.

Calmagnite
Most metallochromic indicators also are weak acids. One consequence of
this is that the conditional formation constant for the metal–indicator com-
plex depends on the titrand’s pH. This provides some control over an indi-
cator’s titration error because we can adjust the strength of a metal–indica-
tor complex by adjusted the pH at which we carry out the titration. Unfor-
tunately, because the indicator is a weak acid, the color of the uncomplexed
indicator also changes with pH.
Figure beside, for example, shows the
color of the indicator calmagite as a
function of pH and pMg, where H2In–,
HIn2–, and In3– are different forms of the
uncomplexed indicator, and MgIn– is the
Mg2+–calmagite complex. Because the
color of calmagite’s metal–indicator com-

plex is red, its use as a metallochromic indicator has a practical pH range of

approximately 8.5–11 where the uncomplexed indicator, HIn 2–, has a blue
color.
Some other indicator known can be used for some cations:

Group IV|Complexometry and Its Application 5

 Application of EDTA Titration

EDTA titration mostly succeeds in every cations. There are some procedure
which used in this kind of analytic gravimetric:

Direct Titration
It is the simplest and the most convenient method used in chelometry. In
this method, the standard chelon solution is added to the metal ion solution
until the end point is detected. This method is analogous to simple acid-base
titrations. E.g.-calcium gluconate injection, calcium lactate tablets and
compound sodium lactate injection for the assay of calcium chloride
(CaCl2.6H2O). Limitations -slow complexation reaction -Interference due
to presence of other ions

Back Titration
In this method, excess of a standard EDTA solution is added to the metal
solution, which is to be analyzed, and the excess is back titrated with a
standard solution of a second metal ion. E.g. - Determination of Mn. This
metal cannot be directly titrated with EDTA because of precipitation of
Mn(OH)2. An excess of known volume of EDTA is added to an acidic
solution of Mn salt and then ammonia buffer is used to adjust the pH to 10
and the excess EDTA remaining after chelation, is back titrated with a
standard Zn solution kept in burette using Eriochrome blackT as indicator.
This method is analogous to back titration method in acidimetry. e.g.- ZnO

Replacement Titration
In this method the metal, which is to be analyzed, displaces quantitatively
the metal from the complex. When direct or back titrations do not give
sharp end points, the metal may be determined by the displacement of an
equivalent amount of Mg or Zn from a less stable EDTA complex.

Mn+2 + Mg EDTA-2 → Mg+2 + Mn EDTA-2

Mn displaces Mg from Mn EDTA solution. The freed Mg metal is then di-

rectly titrated with a standard EDTA solution. In this method, excess quan-
tity of Mg EDTA chelate is added to Mn solution. Mn quantitatively displa-

Group IV|Complexometry and Its Application 6

 ces Mg from Mg EDTA chelate. This displacement takes place because Mn
forms a more stable complex with EDTA. By this method Ca, Pb, Hg may
be determined using Eriochrome blackT indicator.

Indirect Titration
This is also known as Alkalimetric titration. It is used for the determination
of ions such as anions, which do not react with EDTA chelate. Protons from
disodium EDTA are displaced by a heavy metal and titrated with sodium
alkali.
Mn+ + H2X-2 → MX (n-4) + 2H+

Some important elements which could be determined by complexometric

titration are as follows: i) Direct Titration : Analysis of Cu, Mn, Ca, Ba, Br,
Zn, Cd, Hg, Al, Thallium, Sn, Pb, Bi, Vanadium, Cr, Mo, Gallium, Fe, Co,
Ni, and Pd.

B. Application of Complexometry: Determination the hardness of water

Complexometric titration is an efficient method for determining the level of

hardness of water. Caused by accumulation of mineral ions, pH of water is increased.
The Kf during the titration of hard water is reduced because of the reduced amount of
EDTA added.

Figure: End point for the titration of hardness with EDTA using EBT as an indicator; the indicator is: (a) red WINEprior to
the end point due to the presence of the Ca2+–indicator complex; (b) grey-blue at the titration’s end point; and (c) blue after
the end point due to the presence of uncomplexed indicator.

Softening of hard water is done by altering the pH of the water reducing the
concentration of the metal ions present.Could be performed in two phases: Basic pH
for ions with high Kf e.g. Ca2+ and Mg2+

Group IV|Complexometry and Its Application 7

 Hard water is water that has high mineral content (in contrast with "soft water").
Hard water is formed when water percolates through deposits of calcium and magne-
sium-containing minerals such as limestone, chalk and dolomite.
Hard drinking water is generally not harmful to one's health, but can pose seri-
ous problems in industrial settings, where water hardness is monitored to avoid costly
breakdowns in boilers, cooling towers, and other equipment that handles water. In do-
mestic settings, hard water is often indicated by a lack of suds formation when soap is
agitated in water, and by the formation of lime scale in kettles and water heaters.
Wherever water hardness is a concern, water softening is commonly used to reduce
hard water's adverse effects.
Minerals that cause hard water have a wide impact on households. Hard water
interferes with almost every cleaning task from laundering and dishwashing to bathing
and personal grooming. Clothes laundered in hard water may look dingy and feel
harsh and scratchy. Dishes and glasses washed in hard water may become spotted as
they dry. Hard water may cause a film on glass shower doors, shower walls, and bath-
tubs. Hair washed in hard water may feel sticky and look dull.
Calcium

Calcium occurs in water naturally. Seawater contains approximately 400

ppm calcium. One of the main reasons for the abundance of calcium in water is
its natural occurrence in the earth's crust. Calcium is also a constituent of coral.
Rivers generally contain 1-2 ppm calcium, but in lime areas rivers may contains
calcium concentrations as high as 100 ppm. Examples of calcium concentrations
in water organisms: seaweed luctuca 800-6500 ppm (moist mass), oysters appro-
ximately 1500 ppm (dry mass).

In a watery solution calcium is mainly present as Ca 2+ (aq), but it may also

occur as CaOH+ (aq) or Ca(OH)2 (aq), or as CaSO4 in seawater. Calcium is an
important determinant of water harness, and it also functions as a pH stabilizer,
because of its buffering qualities. Calcium also gives water a better taste.
Ca (s) + 2H2O (g) -> Ca(OH)2 (aq) + H2 (g)
This reaction forms calcium hydroxide that dissolves in water as a soda, and
hydrogen gas.

Group IV|Complexometry and Its Application 8

 Calcium is a dietary mineral that is present in the human body in amounts
of about 1.2 kg. No other element is more abundant in the body. Calcium phos-
phate is a supporting substance, and it causes bone and tooth growth, together
with vitamin D. Calcium is also present in muscle tissue and in the blood. It is
required for cell membrane development and cell division, and it is partially res-
ponsible for muscle contractions and blood clotting. Calcium regulates membrane
activity, it assists nerve impulse transfer and hormone release, stabilizes the pH of
the body, and is an essential part of conception. In order to stimulate these body
functions a daily intake of about 1000 mg of calcium is recommended for adults.
This may be achieved by consuming dairy, grains and green vegetables.
Calcium carbonate works as a stomach acid remedy and may be applied to
resolve digestive failure. Calcium lactate may aid the body during periods of
calcium deficiency, and calcium chloride is a diuretic. Hard water may assist in
strengthening bones and teeth because of its high calcium concentration. It may
also decrease the risk of heart conditions. Drinking water hardness must be above
8.4 odH. Calcium carbonate has a positive effect on lead water pipes, because it
forms a protective lead(II)carbonate coating. This prevents lead from dissolving
in drinking water, and thereby prevents it from entering the human body.
Calcium and magnesium ions present as sulfates, chlorides, carbonates, and
bicarbonates cause water to be hard. Water chemists measure water impurities in
parts per million (ppm), but water hardness is often expressed in grains of
hardness per gallon of water (gpg). The two systems can be converted
mathematically. Table 1 gives common classifications for hard water with values
listed in both parts per million and grains per gallon. One grain of hardness is the
amount of calcium and magnesium equal in weight to a kernel of wheat.
Table 1. Hard Water Classifications.

Group IV|Complexometry and Its Application 9

VI. Tools and Materials

A. Tools B. Materials
1. Ipi vitamin bottle 1. Distilled water
2. Colored bottle 2. Seawater
3. Measuring flask 100 mL 3. AgNO3
4. Burette 4. NaCl p.a
5. Erlenmeyer 250 mL 5. K2CrO4
6. Pipettes 6. K2CrO4 5%
7. Volumetric pipette
8. Pikno mass
9. Measuring glass

VII. Flow Chart

A. Making of Na-EDTA ±0,01 M Solution

± 4 g of Na-EDTA ± 0,1 g of MgCl2.H2O

-weighed -weighed

-Entered to volumetric flask 400 ml

-Dilute with distilled water
-Moved into bottle and dilute until 1 L
Na-EDTA ± 0,01 M solution

B.
Determining (standardization) of Na-EDTA ±0,01 M with CaCl2 as standard solution

± 0,0811 g of CaCO3 p.a

-Weighed accurately
-Moved to volumetric flask 100 ml using water
-Added HCl 6 M drop by drop until the gas
stopped (the bubble disappear)
-Dilute with water until boundary line
-Shaked well
CaCl2 ± 0,01 M solution

Group IV|Complexometry and Its Application 10

 25 ml of CaCl2
±0,01 M solution
Na-EDTA ± 0,01 -Entered to volumetric flask 300 ml
M solution
-Added 5 ml of buffer solution (pH:10)
-Entered to burette -Added 3 drops of EBT indicator

-Titrated

Color changes from red

wine to blue

-Read and write down the volume of Na-EDTA

-Calculate the concentration of Na-EDTA
-Repeated 3 times

Average concentration of Na-EDTA

C. Application of Complexometry: Hardness water of PDAM water

10 ml of water
sample (PDAM)
Na-EDTA ± 0,01 -Entered to volumetric flask 300 ml
M solution
-Added 5 ml of buffer solution (pH:10)
-Entered to burette -Added 3 drops of EBT indicator

-Titrated

Color changes from red

wine to blue

-Read and write down the volume of Na-EDTA

-Calculate the Hardness water of sample
-Repeated 3 times

Total hardness water of CaCO3 salt/liter

Group IV|Complexometry and Its Application 11

VIII. Result Of The Experiment
Result of The Experiment Assumption/
Experiment Procedure Conclusion
Before After Reaction
A. Making of Na-EDTA ±0,01 M Solution
Na-EDTA : colorless Na-EDTA : colorless The average
solution solution
± 4 g of Na-EDTA ± 0,1 g of MgCl2.H2O concentration of
Distilled water: Na-EDTA is
weighed weighed colorless solution
0,0123 M and total
Entered to volumetric flask 400 ml hardness of water
Dilute with distilled water
Moved into bottle and dilute until 1 L of PDAM water

Na-EDTA ± 0,01 M solution from Ketintang

Wiyata region
is189 ppm
Determining (standardization) of Na-EDTA ±0,01 M with
B. CaCO3 p.a: white CaCO3 p.a+HCl 6M ⟶
CaCl2 as standard solution
powder colorless solution
± 0,0811 g of CaCO3 p.a
Distilled water: + distilled water ⟶
Weighed accurately colorless solution colorless solution
Moved to volumetric flask 100 ml using
water
Added HCl 6 M drop by drop until the
gas stopped (the bubble disappear)
Dilute with water until boundary line
Shaked well

CaCl2 ± 0,01 M solution

Group IV|Complexometry and Its Application 12
Distilled water: CaCl2+ buffer solution Ca2++Y4- ⟶ CaY2--
colorless solution ⟶ colorless solution

Na-EDTA : colorless +3 drops of EBT ⟶

solution red wine solution

Buffere solution: + Na-EDTA⟶ blue

colorless solution solution

EBT: red wine V Na-EDTA

solution V1= 16,3 ml
V2= 16,5 ml
CaCl2: colorless V3= 16,4 ml
solution

Group IV|Complexometry and Its Application 13

C. Applicat
on of Complexometry: Hardness water of PDAM water Na-EDTA : colorless Sample + buffer Ca2++Y4- ⟶ CaY2--
solution solution ⟶ colorless
10 ml of water solution
sample (PDAM) Buffere solution:
colorless solution +3 drops of EBT ⟶
Entered to volumetric flask red wine solution
300 ml EBT: red wine
Added 5 ml of buffer solution + Na-EDTA⟶ blue
Na-EDTA ± 0,01 M
solution (pH:10) solution
solution Added 3 drops of EBT Sample: colorless
indicator V Na-EDTA
Entered to burette solution
V1= 4 ml
V2= 3,9 ml
Titrated V3= 3,8 ml
Color changes from red
wine to blue

Read and write down the volume of Na-

EDTA
Calculate the Hardness water of sample
Repeated 3 times

Total hardness water of CaCO3 salt/liter

Group IV|Complexometry and Its Application 14
Group IV|Complexometry and Its Application 15
IX. Analysis and Explanation:

Complexometric is a form of volumetric analysis in which the formation of a co-

lored complex is used to indicate the end point of a titration. Complexometric titrations
are particularly useful for the determination of a mixture of different metal ions in
solution.

An indicator capable of producing an unambiguous color change is usually used to

detect the end-point of the titration. In this experiment we will detect Ca2+ in formation
of Complex with Na-EDTA. This experiment we use CaCl 2 as a standard solution,
because it not primary standard so we must make standard solution from this matter.

A.
Determining (standardization) of Na-EDTA ±0,01 M with CaCl2 as standard solution

We use CaCO3 pure analyte to make standard solution CaCl2. Weight accurately
0.0811 gram of CaCO3 p.a (white powder). Moved to volumetric flask 100 ml using water
but not until boundary line, after that add HCl 6M (colourless solution) drop to drop until
the gases is stop.

CaCO3(s) + 2HCl(aq) →CaCl2(aq) + H2O(l) + CO2(g)

Before added HCl the solution is turbid but after added HCl the solution becomes
colorless.The function of adding HCl is to making loosen carbon dioxide, because from
this reaction carbon dioxide which can be seen in the bubble form, calcium chloride, and
water will be formed. If the bubble has completely gone, it means the CaCl2 has been
formed and it can be used to standardization as the analyte.

This Titration used 25 ml of CaCl2 solution entered to Erlenmeyer. Added 5 ml of

buffer solution pH=10, the solution still colorless. The function of the buffer solution pH=
10 addition because in pH 8-10 is a range where dominant form of EBT is in form blue
HIn2- and this titration of CaCl2 and Na-EDTA is in a basic condition during titration.
Buffer solution will defend the pH because this titration needs the constant pH to make
titration process stable. After that, added 3 drops of EBT indicators. The solution changes
color from colorless to red wine. It is suitable with the theory because EBT has red wine in
color (shown in picture below). The reason why using this indicator is because this
indicator forming red wine stable complex 1:1 with some cations such as: Mg2+, Ca2+,

Group IV|Complexometry and Its Application 16

 Zn2+, and Ni2+. Since this titration using CaCO3
as the analyte which contain ion of Ca2+. So,
EBT is suitable to be used in this experiment

The reaction is:

Ca2+ + In3- ⇄ CaIn-

Based on the expe- Based on the theory: Metal ion indicator indicator-metal
riment: the addition of EBT is blue in a buffered
(colorless) (blue) complex(wine-red)
EBT changes the solu- solution at pH 10. It turns
2+
tion to red wine solu- red when Ca ions
tion

After that, titrated the CaCl2 solution with Na-

EDTA solution until the color changes to blue.
It suitable with the theory where EBT in a
buffered solution pH=10 is blue (shown in the
figure beside).The using of EDTA as a titrant
because EDTA forming stable complex, soluble
in water forming complex 1:1 with metal ions.
The reaction is: Based on the expe- Based on the theory:
riment: indicator EBT EBT is blue in a buffered
is blue in a buffered solution at pH 10. It turns
Ca2+ (aq) + EDTA4- (aq) → Ca(EDTA)2- (aq) solution at pH 10. red when Ca2+ ions

The experiment is repeated of three times. The volume of Na-EDTA which

require to turns the color from red wine to blue are 16.3 ml, 16.5 ml, and 16.4 ml. after
that, calculate the concentration of Na-EDTA using equality :

Molek Na-EDTA=Molek CaCO3.

The concentration of Na-EDTA in the first trial is 0.0122 M, in the second trial is
0.0124 M and the third is 0.0123 M. So, the average concentration of Na-EDTA is
0,01M

Group IV|Complexometry and Its Application 17

 B. Application of Complexometry: Hardness water of PDAM water

This application is determine the hardness of water. Here we are using sample of
PDAM water which we took from Ketintang Wiyata region. The PDAM water is used
as the analyte and EDTA as a titer. First, enter 10 ml of sample to Erlenmeyer. Next,
adding 2 ml of buffer solution pH=10. The function of the buffer solution pH= 10
addition because in pH 8-10 is a range where dominant form of EBT is in form blue
HIn2- and this titration of CaCl2 and Na-EDTA is in a basic condition during titration.
Buffer solution will defend the pH because this titration needs the constant pH to make
titration process stable. After that add 3 drops of EBT. The solution changes color from
colorless to red wine. It is suitable with the theory because EBT has red wine in color
(shown in picture below).
The reason why using this indicator is
because this indicator forming red wine stable
complex 1:1 with some cations such as: Mg2+,
Ca2+, Zn2+, and Ni2+. Since this titration has
purpose to determine the level of Ca2+ in the
sample, so EBT is suitable to be used in this
experiment
The reaction is:
Based on the expe- Based on the theory:
riment: the addition of EBT is blue in a buffered Ca2+ + In3- ⇄ CaIn-
EBT changes the solu- solution at pH 10. It turns
tion to red wine solu- red when Ca2+ ions Metal ion indicator indicator-metal
tion
(colorless) (blue) complex(wine-red)

After that, titrated the sample which has been

added by EBT indicator with Na-EDTA
solution until the color changes to blue. It
suitable with the theory where EBT in a
buffered solution pH=10 is blue (shown in the
figure beside).The using of EDTA as a titrant
because EDTA forming stable complex, soluble
in water forming complex 1:1 with metal ions. Based on the expe- Based on the theory:
riment: indicator EBT EBT is blue in a buffered
The reaction is: is blue in a buffered solution at pH 10. It turns
solution at pH 10. red when Ca2+ ions
Ca2+ (aq) + EDTA4- (aq) → Ca(EDTA)2- (aq)

Group IV|Complexometry and Its Application 18

 Initially, indicator is added to a solution containing metal ions. The indicator reacts
with the metal ions in solution to form complex ions, and the solution takes on color of
indicator-metal complex ion. Prior to equivalence point, added EDTA reacts with free
metal ions in solution to form complex ions. The solution color does not change during
this part of the titration. As the equivalence point is approached, added EDTA displaces
metal ions from the indicator-metal complex ion.

The experiment is repeated of three times. The volume of Na-EDTA which

require to turns the color from red wine to blue are 4 ml, 3,9 ml, and 3,8 ml. After that,
calculate the concentration of sample using equation:

Molek of sample = Molek Na-EDTA

From the standardization experiment, we know that the concentration of Na-EDTA is

0,0123 M. From data above, the concentration of sample in the first trial is 0.0049 M, in
the second trial is 0.0047 M and the third is 0.0046 M. So, the average concentration of
sample is 0,0047 M

The next step is determining the hardness of water for each concentration from the
calculation we done before. But, first we have to calculate the mass of Ca 2+ in the
sample using equation:

mass of Ca 1000
M sample= × × dilution factor
Ar Ca 100

In the first trial with concentration of sample is 0,0049 M we get mass of Ca 2+ in the
sample is 0,00196 g. After that calculate the level of Ca2+ in the sample using equation:

Mass of Ca
Level of Ca2+ in water sample ¿
v sample

And we get the level of Ca2+ is 196 ppm. For the second trial, the mass of Ca 2+ in the
sample is 0,00188 g and the level of Ca 2+ in the sample is 188 ppm. Meanwhile, for the
third trial the mass of Ca 2+ in the sample is 0,00184 g and the level of Ca 2+ in the
sample is 184 ppm. So the average level Ca2+ in the sample is 189 ppm.

Group IV|Complexometry and Its Application 19

XI. Conclusion

From the experiment, we can conclude that :

1. The concentration of Na-EDTA standard solution is 0,0123 m

2. The level of Ca2+ in seawater is 189 ppm
X. Question and Answer( standardization)
1. NaC10H16N2O8 and C20H12N3O7SNa
2. Calcium concentrations are measured in units of ppm as calcium, ppm as CaCO 3,
moles per liter, or any other convenient concentration unit. Table 1 indicates some of
the concentration units.
TABLE 1: Concentration Unit Conversion Factors

3. We'll take a mixture of ammonia and ammonium chloride solutions as typical.

Ammonia is a weak base, and the position of this equilibrium will be well to the left:

Adding ammonium chloride to this adds lots of extra ammonium ions. According to
Le Chatelier's Principle, that will tip the position of the equilibrium even further to the
left.
The solution will therefore contain these important things:
 lots of unreacted ammonia;

 lots of ammonium ions from the ammonium chloride;

 Enough hydroxide ions to make the solution alkaline.

Other things (like water and chloride ions) which are present aren't important to the
argument.

Adding an acid to this buffer solution

There are two processes which can remove the hydrogen ions that you are adding.
Removal by reacting with ammonia

Group IV|Complexometry and Its Application 20

The most likely basic substance which a hydrogen ion is going to collide wih is an
ammonia molecule. They will react to form ammonium ions.

Most, but not all, of the hydrogen ions will be removed. The ammonium ion is weakly
acidic, and so some of the hydrogen ions will be released again.

Removal of the hydrogen ions by reacting with hydroxide ions

Remember that there are some hydroxide ions present from the reaction between the
ammonia and the water.

Hydrogen ions can combine with these hydroxide ions to make water. As soon as this
happens, the equilibrium tips to replace the hydroxide ions. This keeps on happening
until most of the hydrogen ions are removed.

Again, because you have equilibria involved, not all of the hydrogen ions are
removed - just most of them.

Adding an alkali to this buffer solution

The hydroxide ions from the alkali are removed by a simple reaction with
ammonium ions.

Because the ammonia formed is a weak base, it can react with the water - and
so the reaction is slightly reversible. That means that, again, most (but not all) of the
the hydroxide ions are removed from the solution.

Group IV|Complexometry and Its Application 21

Question and Answer(application)

1. At a very high pH values, hydroxide ions can penetrate layers of metal coordination,
and complexes such as Cu(OH)Y3- may arise. Clear that in line with the decrease in
pH, the equilibrium moves away, the pH value below by EDTA titration of copper is
not feasible. Solution of the metal ions to be titrated with EDTA buffered to pH
constant despite the release of H3O+ when the complex is formed. At high pH metal
ions tend to hydrolyze and even precipitate as hydroxide.
2. ppm of CaCO3
 Molek of sample = Molek Na-EDTA
M1 x V1 = Me xVe
M1 x 100 ml = 0,01016 M x 15,28 ml
M1 = 0,00155 M
Determination hardness of water of sample (PDAM)
mass of Ca 1000
 M sample= × × dilution factor
Ar Ca 100
mass of Ca 1000
0,00155= × ×1
40 100
Mass of Ca2+ = 0,0621 g

Mass of Ca 0,0621
Level of Ca2+ in water sample ¿ = =¿0,000621 g/mL
v sample 100
= 621 mg/L

= 621 ppm

ppm MgCO3

 Molek of sample = Molek Na-EDTA

M1 x V1 = Me xVe
M1 x 100 ml = 0,01016 M x 10,43 ml
M1 = 0,00106M
Determination hardness of water of sample (PDAM)
mass of Mg 1000
M sample= × × dilution factor
Ar Mg 100

Group IV|Complexometry and Its Application 22

 mass of Mg 1000
0,00106= × ×1
24 100
Mass of Mg2+ = 0,0254 g

Mass of Mg 0,0254
Level of Mg2+ in water sample ¿ = =¿ 0,000254 g/mL
v sample 100
= 254 mg/L

= 254 ppm

XI. Referencess
Day, R.A, Jr & Underwood, A.L. 2002. Analisis Kimia Kuantitatif: Edisi keenam..
Translated Iis Sopyan. Jakarta: Erlangga

Larsen, Delmar PhD .2014.9C Complexation Titration.(online),(

http://chemwiki.ucdavis.edu/Analytical_Chemistry/Analytical_Chemistry_2.0/
09_Titrimetric_Methods/9C_Complexation_Titrations, accessed on December
19th, 2014)

Noname.2013.Complexometry, (online),
(http://www.en.wikipedia.org/wiki/complexometry , accessed on December
19th, 2014)

Noname.2013.EDTA, (online),(http://www.en.wikipedia.org/wiki/EDTA , accessed

on December 19th, 2014)

Svehla, G.(1985). Vogel: Buku Teks Analisis Oraganik Kualitatif Makro dan
Semimikro.(first edition). Translated Setiono, L and Handayana, P.A Jakarta:
Kaliman Media Pusaka.

Tim Kimia Dasar. 2014. Panduan Praktikum Kimia Analitik I Dasar-Dasar Kimia
Analitik. Surabaya: Jurusan Kimia FMIPA Unesa

Group IV|Complexometry and Its Application 23

Attachment 1

A.
Determining (standardization) of Na-EDTA ±0,01 M with CaCl2 as standard solution

Entered CaCO3 (white Dilute with distilled water

HCl 6 M
powder) into volumetric until boundary line
Colorless solution
flask Turbid solution

Took 25 ml of CaCl2 and

CaCO3 + distilled water
White precipitate
Addition of HCl 6M
moved to Erlenmeyer
Producing bubble
Colorless solution
Group IV|Complexometry and Its Application 24
Addition of buffer solution Addition of EBT Indicator Titration process with Na-
pH=10 Red wine solution EDTA
Colorless solution

After reaching the endpoint

V1= 16,3 ml V2=16,4 ml V3=16,5 ml
Blue Solution

Group IV|Complexometry and Its Application 25

B. Application of Complexometry: Hardness water of PDAM water

Addition of buffer solution Addition of EBT Indicator

10 ml of Sample (PDAM)
pH=10 Red wine solution
Colorless solution
Colorless solution

10 ml sample + buffer solution pH=10+ EBT indicator

Red wine solution

Group IV|Complexometry and Its Application 26

 After reaching the endpoint
Titration process with Na-EDTA
Blue Solution

After reaching the endpoint

V1Group
= 4 mlIVV|Complexometry
2= 3,9 ml V3= 3,8 ml
and Its Application 27
Blue Solution
Attachment 2

A.
Determining (standardization) of Na-EDTA ±0,01 M with CaCl2 as standard solution

Reaction : Ca2++Y4- ⟶ CaY2—

Mass of CaCO3 : 0,0811 g
Mr of CaCO3 : 100
Determining the concentration of Ca2+

mass of CaC O3 1000

2 +¿= × ¿
Mr CaC O3 100
MCa

0,0811g 1000
2 +¿= × ¿
100 100
MCa

2 +¿=0,00811 M ¿
MCa

V Na-EDTA : V1= 16,3 ml

V2= 16,5 ml
V3= 16,4 ml

 Determining the concentration of Na-EDTA

 Molek Na-EDTA = Molek CaCO3
M1 x V1 = M2 xV2
M1 x 16,3 ml = 0,0811 M x 25 ml
M1 = 0,0124 M
 Molek Na-EDTA = Molek CaCO3
M1 x V1 = M2 xV2
M1 x 16,4 ml = 0,0811 M x 25 ml
M1 = 0,0123 M
 Molek Na-EDTA = Molek CaCO3
M1 x V1 = M2 xV2
M1 x 16,5 ml = 0,0811 M x 25 ml
M1 = 0,0122 M
0.0124+ 0,0123+0,0122
 Average concentration of Na-EDTA =
3

Group IV|Complexometry and Its Application 28

 = 0,0123 M

B. Application of Complexometry: Hardness water of PDAM water

Reaction : Ca2++Y4- ⟶ CaY2—

M Na-EDTA : 0,0123 M
V Na-EDTA : V1= 4 ml
V2= 3,9 ml
V3= 3,8 ml
 Determination the concentration of sample (PDAM)
 Molek of sample = Molek Na-EDTA
M1 x V1 = Me xVe
M1 x 10 ml = 0,0123 M x 4 ml
M1 = 0,0049 M
 Molek of sample = Molek Na-EDTA
M2 x V2 = Me xVe
M2 x 10 ml = 0,0123 M x 3,9 ml
M1 = 0,0047 M
 Molek of sample = Molek Na-EDTA
M3 x V3 = Me xVe
M3 x 10 ml = 0,0123 M x 3,8 ml
M3 = 0,0046 M
0.0049+0,0047+ 0,0046
 Average concentration of sample =
3
= 0,0047 M
 Determination hardness of water of sample (PDAM)
mass of Ca 1000
 M sample= × × dilution factor
Ar Ca 100
mass of Ca 1000
0,0049= × ×1
40 100
Mass of Ca2+ = 0,00196 g

Mass of Ca 0,0196
Level of Ca2+ in water sample ¿ = =¿ 0,000196 g/mL
v sample 10
= 196 mg/L

Group IV|Complexometry and Its Application 29

 = 196 ppm

mass of Ca 1000
 M sample= × × dilution factor
Ar Ca 100
mass of Ca 1000
0,0047= × ×1
40 100
Mass of Ca2+ = 0,00188 g

Mass of Ca 0,0188
Level of Ca2+ in water sample ¿ = =¿0,000188 g/mL
v sample 10
= 188 mg/L

= 188 ppm

mass of Ca 1000
 M sample= × × dilution factor
Ar Ca 100
mass of Ca 1000
0,0046= × ×1
40 100
Mass of Ca2+ = 0,00184 g

Mass of Ca 0,0184
Level of Ca2+ in water sample ¿ = =¿0,000184 g/mL
v sample 10
= 184 mg/L

= 184 ppm

196+188+184
 Average level of Ca2+ in sample (PDAM) =
3
=189 ppm

Group IV|Complexometry and Its Application 30