A.

TITLE
B. PURPOSE

: Complexometry Titration and its Application

: 1. To make and determine (standardization) of Na-EDTA

solution
2. To determine the total hardness of Kenjeran well water
C. BASIC THEORY :
Complexometry Titration
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.
Basic theory of complexometry titration with EDTA is the forming of
complex compound between some metal (such as: Ca, Mg, Ni, Zn, Cu, etc) with
EDTA. Metals will forms complex with EDTA at different pH, Ca 2+ and Mg2+ react
well at pH 8 10. EDTA (Etilen Diamine Tetra Acetate) is an acid base 4 (H 4Y). but,
which is often used is the natrium salt (Na2H2Y). the forming of complex between
metals ions and EDTA according to pH of solution. Indicator that is used are EBT
(Enochrome Black T) and Kalgamit. That indicator is a weak acid basic 3 (H 3In).
dissociating equilibrium of that indicator will give some colors and forming complex
1 : 1 with total metal ion, so, can give the color change at the end of reaction.
Reactions

: H2In- HIn2- + H+
Red
Blue
With metal ion
: Ca2+, Mg2+, Zn2+, Ni2+:
Mg2+ + HIn2- MgIN- + H+
Red grape
With EDTA : MgIn- + H2Y2- MgH2Y2- MgH2Y + In3Red grape
In3- + H2O HIn- + OHBlue
At equivalent point:
Sum of equivalent Mg2+ = sum of equivalent EDTA
Indicator

Complexometry Titration

So, the changing color through titration is : solution that contain of metal ion
like the statement above after added by EBT indicator will be change into red grape,
after that, after theres happen an equivalent between metal ion with EDTA can be
seen from the form of blue from indicator in HIn2-.
In theory, any complexation reaction can be used as a volumetric technique
provided that:
1. The reaction reaches equilibrium rapidly after each portion of titrant is added.
2. Interfering situations do not arise. For instance, the stepwise formation of
several different complexes of the metal ion with the titrant, resulting in the
presence of more than one complex in solution during the titration process.
3. A complexometric indicator capable of locating equivalence point with fair
accuracy is available.
In practice, the use of EDTA as a titrant is well established.

Reagent 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
coordinate covalent bonds to metal cations makes EDTA a hexadentate ligand.
However, in practice EDTA is usually only partially ionized, and thus forms fewer
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

Complexometry Titration

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, M2+, 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 formation of the
metal cation-EDTA complex goes to completion, and this is chiefly why EDTA is
used in titrations / standardizations of this type.
Indicators
To carry out metal cation titrations using EDTA, it is almost always necessary
to use a complexometric indicator to determine when the end point has been reached.
Common indicators are organic dyes such as Fast Sulphon Black, Eriochrome 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 endpoint has been reached. Thus, the free indicator (rather than the metal
complex) serves as the endpoint indicator. The end point of this titration is the change
from blue color (EBT) to colorless. and when EBT form weak complex with the ca
and mg ion present in the solution but after the addition with titration with EDTA all

Complexometry Titration

the metal ion leaving EBT which formed weak and unstable compound react with
EDTA forms stable and stable complex.
Well Water
Shallow pumping wells can often supply drinking water at a very low cost,
but because impurities from the surface easily reach shallow sources, a greater risk of
contamination occurs for these wells when they are compared to deeper wells.
Chemical contamination is a common problem with groundwater. Nitrates
from sewage or fertilizer are a particular problem for children. Pollutant chemicals
include pesticides and volatile organic compounds from gasoline, dry-cleaning, the
fuel additive methyl tert-butyl ether (MTBE), and perchlorate from rocket fuel, airbag
inflators, and other artificial and natural sources.
Several minerals are also contaminants, including lead leached from brass
fittings or old lead pipes, chromium VI from electroplating and other sources,
naturally occurring arsenic, radon, and uraniumall of which can cause cancerand
naturally occurring fluoride, which is desirable in low quantities to prevent tooth
decay, but can cause dental fluorosis in higher concentrations.[8]
Some chemicals are commonly present in water wells at levels that are not
toxic, but can cause other problems. Calcium and magnesium cause what is known as
hard water, which can precipitate and clog pipes or burn out water heaters. Iron and
manganese can appear as dark flecks that stain clothing and plumbing, and can
promote the growth of iron and manganese bacteria that can form slimy black
colonies that clog pipes.

Complexometry Titration

Hard Water/ Hardness Water

Hard water is water that has high mineral content (in contrast with "soft
water"). Hard drinking water is generally not harmful to one's health,[1] but can pose
serious problems in industrial settings, where water hardness is monitored to avoid
costly breakdowns in boilers, cooling towers, and other equipment that handles water.
In domestic settings, hard water is often indicated by a lack of suds formation when
soap is agitated in water, and by the formation of limescale in kettles and water
heaters. Wherever water hardness is a concern, water softening is commonly used to
reduce hard water's adverse effects.
Water's hardness is determined by the concentration of multivalent cations in
the water. Multivalent cations are cations (positively charged metal complexes) with a
charge greater than 1+. Usually, the cations have the charge of 2+. Common cations
found in hard water include Ca2+ and Mg2+. These ions enter a water supply by
leaching from minerals within an aquifer. Common calcium-containing minerals are
calcite and gypsum. A common magnesium mineral is dolomite (which also contains
calcium). Rainwater and distilled water are soft, because they contain few ions.[2]
The following equilibrium reaction describes the dissolving/formation of
calcium carbonate scale:
CaCO3 + CO2 + H2O Ca2+ + 2HCO3
Calcium carbonate scale formed in water-heating systems is called limescale.
Calcium and magnesium ions can sometimes be removed by water softeners.

Complexometry Titration

Temporary hardness is a type of water hardness caused by the presence of

dissolved bicarbonate minerals (calcium bicarbonate and magnesium bicarbonate).
When dissolved these minerals yield calcium and magnesium cations (Ca2+, Mg2+)
and carbonate and bicarbonate anions (CO32-, HCO3-). The presence of the metal
cations makes the water hard. However, unlike the permanent hardness caused by
sulfate and chloride compounds, this "temporary" hardness can be reduced either by
boiling the water, or by the addition of lime (calcium hydroxide) through the
softening process of lime softening. Boiling promotes the formation of carbonate
from the bicarbonate and precipitates calcium carbonate out of solution, leaving water
that is softer upon cooling.

D. Tools and materials

:
Volumetric flask 500 mL
Pipette
Volumetric pipette
Erlenmeyer
Burette
CaCO3
Aquades
HCl
Na-EDTA solution 0,01 M
CaCl2 solution
EBT

Complexometry Titration

E. PROCEDURE :
Determination of standardization Na-EDTA solution 0,01 M with CaCl 2
as standard solution

- Moved
0,4 grams
of into the volumetric flask 500 mL used water 100
CaCO3mL
-

Added HCl 1 : 1 drop by drop until gladak gas stopped

Diluted with water until the limit sign
Shake until mixed perfectly
Washed and filled with Na-EDTA solution 0,01 M
Pipette with volumetric pipette 50 mL of CaCl2 solution
Entered into the Erlenmeyer 300 mL
Added 5 mL of buffer solution pH 10
Added 5 drops of EBT indicator
Titrated with Na-EDTA solution 0,01 M
Stopped titration when theres changing color from redish
grape to blue

Changing- Color
Read and note the number on burette when the first and the

end of titration
Determine and note Na-EDTA solution that used in titration
Calculated the mean concentration of Na-EDTA

The mean
concentration of
Na-EDTA
Determination
the sum of the hardness of Kenjeran well water

25 mL of sample
- Pipette and dropped to Erlenmeyer
water

Added 2 mL buffer solution pH 10

Added 3 drops of BET
Titration with EDTA 3x

Complexometry Titration

Blue (preciously
until red
- color
disappear)

Calculated the sum of the hardness in CaCO3 salt per liter of

water (in the form of ppm)

Average hardness of well water

Complexometry Titration

F. EXPERIMENT RESULT
No
.
1.

Procedure of Experiment

Determination of standardization
Na-EDTA solution 0,01 M with
CaCl2 as standard solution
0,4 grams of
CaCO3

Moved into the

volumetric flask 500
mL used water

100 mL
Added HCl 1 : 1
drop by drop until

gladak gas stopped

Diluted with water

until the limit sign

Shake until mixed

perfectly
Washed and filled
with Na-EDTA

solution 0,01 M
Pipette with volume-

Experiment
result
Before:

Erlenmeyer 300 mL
Added 5 mL of
buffer solution pH

10
Added 5 drops of

Complexometry Titration

Conclusion

CaCO3(s)

Na-EDTA

CaCO3
powder:white

+H2O(l)CaCO3

concentration is

(aq) .

Aquades
:colorless

CaCO3(s)

0.0106 M

HCl solution:
colorless
Buffersolution:c
olorless
EBT Indicatior:
dark purple (red
wine)
Na-EDTA:
colorless
After:
CaCO3 solution:
turbid
Buffer solution
+CaCl2:
colorless

tric pipette 50 mL of Buffer solution

CaCl2 solution
Entered into the

Hypothesis

+CaCl2+EBT:
reddish grape

After titrated by
Na-EDTA:
reddish grape
to blue
V1EDTA: 8 mL
V2EDTA: 7.5 mL

+2HCl(aq)CaCl2(
+CO2(g) + H2O(l)
Ca2++Y4- CaY2aq)

V3EDTA: 7.3 mL

EBT indicator
Titrated with NaEDTA solution 0,01

M
Stopped titration
when theres
changing color from
redish grape to blue

Changing
- Color
Read and note the

number on burette
when the first and
-

the end of titration

Determine and note
Na-EDTA solution

that used in titration

Calculated the mean
concentration of NaEDTA

The mean
concentration of NaEDTA

2.

Determination the hardness of

well water
25 mL of sample
water

Complexometry Titration

Well water from

kenjeran:
colorless

10

The total of
hardness well
water in

Buffersolution:c
olorless

Pipette and dropped

to Erlenmeyer
Added 2 mL buffer

solution pH 10
Added 3 drops of

EBT Indicatior:
dark purple (red
wine)

BET
Titration with EDTA

Na-EDTA:
colorless

3x

Blue (preciously
until red color
disappear)

Calculated the sum of

the hardness in
CaCO3 salt per liter of
water (in the form of
ppm)

The average hardness

water of well water

After:
Buffer solution
+well water:
colorless
Buffer solution
+well
water+EBT:
reddish grape
After titrated by
Na-EDTA:
reddish grape
to blue
V1EDTA:1. 8 mL
V2EDTA: 2.2 mL
V3EDTA: 2.0 mL

Complexometry Titration

11

kenjeran is
210.6 ppm

G. ANALYSIS AND DISCUSSION

a. Determination of Standardization Na-EDTA 0,01 M with CaCO 3 as
primery standard solution.
In the experiment that we have done, we used 0,081 grams of white
powder CaCO3, then we poured into volumetric flask, then we add aquadest.
The reaction that occur is :
CaCO3(s) + H2O(l) CaCO3(aq) .
After that we add HCl 6M, 1:1 drops by drops until the bubbles
disappear (CO2 lose). And then we dilute with aquadest again until formed
CaCl2 solution. The reaction that occur in this step is :
CaCO3(s) + 2 HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)
To know that CO2 is lose we observe with there is changes from turbid
become clear solution. After that we pipette 10 ml of CaCl 2 solution 1ml of
buffer solution. And we add 2 drops of EBT indicators. In the basic, this
titration formed complex ions, Ca2+ with EDTA.
EDTA is a chelating agent that can donate electrons (Lewis rule)
which would then form a complex with the metal ion (Lewis acid). EDTA will
first form a complex with Ca2 +. As in any titration we will need an indicator
to determine when all the Ca 2 + has formed a complex with EDTA (endpoint).
The metals will form complex with EDTA in different pH. Ca 2+ react
well in pH between 8 until 10.Forming of complex between metallic ions with
EDTA depends on pH solution. In this titration we use EBT (Erichrome Black
T). This indicator is include weak acid that have base 3 (H 3In). Balancing of
disotiation indicator will give different color and form complex 1:1 with
amount of metallic ions, so it will give different color in the end of titration.
The changes color in the titration is solution that contain metallic ions
of Ca2+ after adding EBT is become red grape. Then after in the eqivalent
point, between metallic ions of Ca2+ with EDTA can we observe from solution
become blue and indicators in the form of HIn2-.
The reaction in EBT indicator :
H2In- Hin2- + H+
Red blue

Complexometry Titration

12

With metallic ion: Ca2+ so it become

Ca2+ + Hin2-CaIn- + H+
Red wine
With EDTA : CaIn- + H2Y2- CaH2Y2- CaH2Y + In3Red Wine
In3- + H2O HIn- + OHBlue
Then the solution titrated with Na-EDTA. We stopped where there is
changes of color from red wine become blue. The reaction that occur is :
Ca2+ + Y4- CaY2The blue color that occur due to titrant is a mixture of MgY2- and Y4-.
When

the mixture

the more- stable will

was added to a
be

formed by

solution containing Ca2+, CaY2free Mg2+

to react with the

indicator (EBT) and- form red MgIn-.

After the calcium is used in full, additional titrant change MgIn- and
MgY2 indicator turns into a blue HIn2-form. In this experiment we got NaEDTA 8 ml, 7.5 ml, and 7.3 ml. Then we calculate molarity of Na-EDTA
using formula
mmol Na-EDTA = mmol CaCO3.
The molarity of Na-EDTA that we get is 0,0101 M, 0,0108 M, 0,011
M and the average of Na-EDTA concentration is 0.0106 M.

Complexometry Titration

13

b. Determining Total Hardness Of Well Water.

In the determination total hardness of well water, pipette 10 mL of
well water and moved into Erlenmeyer 250 mL, then add 1 mL of buffers
solution pH 10 in the form of clear colorless solution and 2 drops of EBT
indicator with the red grape color. Then titrated with Na-EDTA solution until
the analyte solution changed color into blue. The change color into blue it
show that the end point titration is reach . Repeat the experiment 3 times than
we can get the average total hardness water .
Using equation :
mmol sample = mmol EDTA
We got mmol well water sample which are used to determine the
mass of Ca2+. Mass Ca2 obtained is used to determine the hardness of well
water by divided mass of Ca2 (gr) and well water volume (sample volume)(l).
So, by using that equation the hardness water we got are 190ppm,
230ppm, 212ppm and the average of the hardness water are 210.6 ppm.

H. CONCLUSION
Based on experiment that we have done, we can conclude that :
1. Na-EDTA concentration is 0.0106 M
2. The total of hardness well water in kenjeran is 210.6 ppm

Complexometry Titration

14

I. ANSWER OF QUESTION
Making and Determining (standardization) of Na-EDTA solution.
1) Find the chemical formula of Na-EDTA, Black Eriokrom T!
Answer:
The chemical formula of Na-EDTA is

The chemical formula of Black Eriokrom T is

2) What is the concentration of CaCl2 solution if it is expressed with ppm

CaCO3?
Answer:
CaCO3 + 2 HCl CaCl2 + H2O + CO2
Mass CaCO3

0,081 gram

81,0 mg

Volume CaCO3

100 mL

0,1 L

Concentration of CaCO3 in ppm =

m
V

ppm =

ppm

Complexometry Titration

15

81,0 mg
0,1 L

ppm = 810

3) How to make buffer solution of ammonia + ammonia chloride with pH

10? Show the calculation!
Answer:
NH3 + HCl
NH4Cl
NH4OH + NH4Cl buffer
kb [ Basa ]
[Garam]
[OH-]

k b [ NH 4 OH ]
[ NH 4 Cl ]
=

1,8 x 10 5 x [ NH 4 OH ]
[ NH 4 Cl ]
=
pH =

14 pOH

10 =

14 pOH

pOH

pOH

- log [OH-]

- log [OH-]

[OH-] =

10-4

1,8 x 10 5 x [ NH 4 OH ]
[ NH 4 Cl ]
10-4=

Complexometry Titration

16

[ NH 4 OH ]
[ NH 4 Cl ]

1,8 x 10 5
10 4

[ NH 4OH ]

gr
Mr . V

=
gr
35 . V

1,8 x 10-5

6,3 x 10-4 . V=

gr

supposed VNH4OH =1 L
so, gr

[ NH 4OH ]

[ NH 4 Cl ]

=6,3 x 10-4 gram

gr
Mr . V

=
gr
Mr . V

Application of Complexometri Titration

1. Why the pH of a solution is the important factor in choosing indicator for
complexiometry titration?
Answer: The selection of indicators related to the use of pH, as required
indicators that renponsif against pMg, pCa, PCU, and p the other,
and because of the indicator should be releasing metal ions on
EDTA at a pM value that is very close to pM values at the
equivalence point.

Complexometry Titration

17

2. A 100 mL of sample water containing ions Ca 2+ and Mg 2+ is titrated with

15.28 mL of 0.01016 M EDTA in an ammonia buffer pH 10. Another
example is 100 mL titrated with NaOH to precipitate Mg (OH)2 and then
titrated to pH 13 with 10.43 mL of the same EDTA solution. Calculate
how ppm CaCO3 and MgCO3 in the sample?
Answer:
Known :
VEDTA 1 = 15,28 mL
MEDTA
VEDTA 2

= 0,01016 M
= 10,43 mL

(V1 V2) EDTA= 15,28-10,43=4,85 mL

Asked :ppm CaCO3 dan ppm MgCO3
Answered:

ppm CaCO3
mmol CaCO3

=mmol EDTA
=( M x V ) EDTA
=0,01016 x 10,43
=0,1059 mmol

mg CaCO3 =mmol x Mr
=0,1059 x 100
=10,59 mg
10,59 mg
0,1 L

ppm CaCO3=
=105,9 mg/L

Complexometry Titration

18

 ppm MgCO3
mmol MgCO3=mmol EDTA
=[ M x (V1 V2)] EDTA
=0,01016 x 4,85
=0,0493 mmol
mg MgCO3=mmol x Mr
=0,0493 x 84
=4,1412 mg
4,1412 mg
0,1 L

ppm MgCO3=
=41,412 mg/L

Complexometry Titration

19

J. REFERENCE
Husain, Asif. 2007. Theoritical Basis of Analysis Complexometric Titration. New
Delhi
http://amrita.vlab.co.in/ Accessed on Monday, December 16th 2013
http://en.wikipedia.org/wiki/Complexometric_titration, December 16th 2013
http://en.wikipedia.org/wiki/Water_well Accessed on Friday, 27th 2013 at 11.23
http://en.wikipedia.org/wiki/Hard_water Accessed on Friday, 27th 2013 at 11.38
Tim.2013.Panduan Praktikum Kimia Analitik I Dasar-Dasar Kimia Analitik.
Surabaya:Jurusan Kimia FMIPA UNESA

Complexometry Titration

20

K. ATTACHMENT
PICTURE

EXPLANATION

Detrmining Standarization Na-EDTA Solution 0.01M With CaCl2 As Primary

Standard Solution
CaCl2 after adding by Erichrome
Black T (EBT)

CaCl2 after titrated by Na-EDTA

solution it change became blue

Determining total Hardness Water of Well Water

Well water after adding by (EBT)
Erichrome Black T

Complexometry Titration

21

Well Water after titrated by NaEDTA solution it change became

blue

Complexometry Titration

22

L. CALCULATION
Determining standardization Na-EDTA solution 0.01 with CaCl2 as primary
standard solution.
Known :
mass of CaCO3=0.081 gr
volume of CaCO3=10 mL
V1EDTA= 8 mL
V2EDTA=7.5 mL
V3EDTA= 7.3 mL
Mr CaCO3 = 100
V of CaCO3 dilution=100 mL=0.1
Reaction :
CaCO3(s) + 2 HCl(aq) CaCl2(aq) + CO2(g) + H2O(l)

Ca2+ + Y4- CaY2Answer:

gr
0.081
=
=0.0081 M
M CaCO3= Mr . L 100.0.1

1. At V EDTA 8 mL
mmol CaCO3 = mmol EDTA
M1. V1 = M2.V2
0.0081 . 10 = M2 . 8
M2= 0.0101 M
2. At V EDTA 7.5 mL
mmol CaCO3 = mmol EDTA
M1. V1 = M2.V2
0.0081 . 10 = M2 7.5
M2= 0.0108 M

Complexometry Titration

23

3. At V EDTA7.3 mL
mmol CaCO3 = mmol EDTA
M1. V1 = M2.V2
0.0081 . 10 = M2 . 7.3
M2= 0.011 M
Average

of

NA-EDTA

Concentration

0.0101 M +0.0108 M + 0.011 M

=0.0106 M
3

Application of Complexometry Titration

Known :
M Na-EDTA=0.0106 M
Mr CaCO3 = 100
Sample volume=10Ml
V1EDTA:1. 8 mL
V2EDTA: 2.2 mL
V3EDTA: 2.0 mL
Answer :
1. At V EDTA 1.8 mL
V Na-EDTA. M Na-EDTA = V Ca2+ . M Ca2+

1.8. 0.0106 = 10 . M Ca2+

Mass of Ca2+

M Ca2+= 1.9 x 10-3

= mmol Ca2+x Mr CaCO3

=1.9 x 10-3 x 1.0 x 10-2 x 100

=1.9 x 10-3 g
=1.9 mg
mass ( mg )
1.9
=
=190 ppm
Hardness of well water = V sample ( L ) 0.01
2. At V EDTA 2.2 mL

V Na-EDTA. M Na-EDTA = V Ca2+ . M Ca2+

2.2. 0.0106 = 10 . M Ca2+

Mass of Ca

2+

M Ca2+= 2.3 x 10-3

= mmol Ca2+x Mr CaCO3

Complexometry Titration

24

=2.3 x 10-3 x 1.0 x 10-2 x 100

=2.3 x 10-3 g
=2.3 mg
mass ( mg )
2.3
=
=230 ppm
Hardness of well water = V sample ( L ) 0.01

3. At V EDTA 2.0 mL

V Na-EDTA. M Na-EDTA = V Ca2+ . M Ca2+

2.0. 0.0106 = 10 . M Ca2+

Mass of Ca2+

M Ca2+= 2.12 x 10-3

= mmol Ca2+x Mr CaCO3

=2.12 x 10-3 x 1.0 x 10-2 x 100

=2.12 x 10-3 g
=2.12 mg
mass ( mg )
2.12
=
=212 ppm
Hardness of well water = V sample ( L ) 0.01

The total average of hardness well water is =

190+ 230+ 212

=210.6 ppm
3

The limit of tolerant hardness water is about 50-80 ppm and our
hardness water is 210.6 ppm, so our hardness water is higher than the tolerant
limit.

Complexometry Titration

25