A.

Title
Complexiometry Titration

B. Date of Experiment
Start : 20 Desember 2011,at 8.00 AM Finish : 20 Desember 2011, at 11.30 AM

C. Objectives
a. Standardization of Na-EDTA solution with CaCO3 as primery standard b. Determine hardness of well water

D. Basic Theory
One way of determining levels of metal ions on the formation of a complex compound between the metal ion complex-forming compounds is by complexiometric titration. Complex-forming compounds as electron donors whereas metal ions that act as electron acceptors. In alkaline solution, complex formation is more efficient and more stable. However, if too alkaline, should really pay attention to the formation of oxidized metal deposition. Complexiometric Titration namely titration based on the formation of complex compounds (ion complex or salt that are hard to ionizes), Complexiometric is a type of titration in which the titrant and analyte complexed each other, forming a complex result. The reactions of complex formation or which involves many complex and its application are also many, not only in the titration. Because it needs a fairly broad understanding of the complex, although here it will first be applied on titrations. Basic requirements in complexiometric titration is neutral complex formation molecule that dissociates in solution is the solubility of high-level, such as metal complexes with EDTA. One type of chemical reaction that serves as a basis for determining titrimetric involves the formation (formation) complex or complex ion which dissolves but slightly dissociated. The complex is referred to here is the complex formed by reaction of metal ions, a cation, with an anion or neutral molecule. Titration complexiometric also known as reaction formation reaction involves complex ions or the formation of a neutral molecule that dissociates in solution. Such complex formation is a fundamental requirement is a high level of solubility. In addition to ordinary complex titration as above, also known complexiometric, as it involves the use of EDTA.

EDTA is potentially a sexidente ligand which may coordinate with a metal ion through its two nitrogens and four carboxyl groups. EDTA or

ethylenediaminetetraacetic acid is a novel molecule for complexing metal ions. It is a polyprotic acid containing four carboxylic acid groups (acidic hydrogens are red) and two amine groups with lone pair electrons (green dots). The classic structural formula is given below. EDTA is synthesized on an industrial scale from ethylenediamine,

formaldehyde, and a source of cyanide (HCN or NaCN. The structure of EDTA :

Ethylene diamine tetra acetic acid or more commonly known as EDTA, is one type of amine polycarboxylic acid. EDTA is actually seksidentat ligand that can coordinate with a metal ion through both nitrogen and fourth of his or carboxyl group called multidentat ligands containing more than two coordination atoms per molecule, such as 1,2-diaminoetanatetraasetat acid (asametilenadiamina tetraasetat, EDTA) which has two nitrogen atoms - contributor and four oxygen donor atoms in a molecule. For more convenience, free acid form of EDTA (Ethylene Diamine Tetra Acetic Acid) is often abbreviated H4Y. But that is often used is the sodium salt (Na2H2Y). The solution is quite acidic, partly protonisasi EDTA without total disintegration of metal complexes can occur, leading to species such as CuHY-, but in general the condition that the four hydrogen disappeared armpit ligand coordinated with a metal ion. At a very high pH values, hydroxide ions can penetrate the layer of metal coordination, and complexes such as Cu (OH) Y3-can arise. For a variety of metal ions and chelating Bahn like EDTA, the value of equilibrium constant for these reactions can be formulated as follows: Mn+ + Y4- MY-(4-n) Kabs =

Kabs-called absolute stability constant or formation constant absolute.

Complex formation between metal ions with EDTA depends on the pH of the solution. At pH values greater majority EDTA was present as tetraanion Y4-. At lower pH values, species-that terprotonisasi HY3 etc, become dominant. It can be seen that the H3O+ compete with metal ions to EDTA, and it is clear that a real tendency to form a brown metal at any pH value can not be seen directly from Kabs. Titration can be determined by the addition of a useful indicator as a sign of the titration endpoint is reached. There are five conditions of a metal ion indicator can be used in the visual detection of the end points of the color reaction should be such that before the end point, when almost all metal ions have been berkompleks with EDTA, the solution will be a strong color. Second, it must be specific color reactions (specific), or at least selectively. Third, the metal-indicator complex should have a fairly stable, if not, because of dissociation, will not obtain a sharp color change. However, the metal-indicator complex should be less stable than the metal-EDTA complexes to ensure that the end point, EDTA remove metal ions from metalindicator complex to the metal-EDTA complex must be sharp and quick. Fifth, the color contrast between free and complex indicators-indicators of metal should be such so easily observed. Indicators need to be very sensitive to metal ions, so that the color change occurs as little as possible with the equivalent point. Finally, the determination of Ca and Mg can be performed by EDTA titration, pH for the titration was 10 with the indicator Eriochrome Black T (EBT). At high pH 12, Mg (OH)2 will precipitate, so that EDTA can be consumed only by Ca2+ with the indicator murexide. Hard water is water that has high mineral content (in contrast with "soft water"). Hard water is generally not harmful to one's health, 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. 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+ 2+

. Usually, the cations have the charge of

2+ 2+

. Common cations

found in hard water include Ca

and Mg . 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 also contain few ions. The following equilibrium reaction describes the dissolving/formation of calcium carbonate scales: CaCO3 + CO2 + H2O Ca2+ + 2HCO3Calcium and magnesium ions can sometimes be removed by water softeners. Temporary hardness is a type of water hardness caused by the presence of dissolved carbonate minerals (calcium carbonate and magnesium carbonate). 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 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. Permanent hardness is hardness (mineral content) that cannot be removed by boiling. When this is boiling the case, it is usually caused by the presence of calcium and magnesium sulphates and/or chlorides in the water, which become more soluble as the temperature rises. Despite the name, the hardness of the water can be easily removed using a water softener, or ion exchange column. Hardness can be quantified by instrumental analysis. The total water hardness, including both Ca2+ and Mg2+ ions, is reported in parts per million (ppm) or mass/volume (mg/L) of calcium carbonate (CaCO3) in the water. Although water hardness usually measures only the total concentrations of calcium and magnesium (the two most prevalent divalent metal ions), iron, aluminium, and manganese can also be present at elevated levels in some locations. The presence of iron characteristically confers a brownish (rust-like) colour to the calcification, instead of white (the color of most of the other compounds). Because it is the precise mixture of minerals dissolved in the water, together with the water's pH and temperature, that determines the behavior of the hardness, a single-number scale does not adequately describe hardness. Descriptions of hardness correspond roughly with ranges of mineral concentrations: Soft : 060 mg/L

Moderately hard Hard Very hard

: : :

61120 mg/L 121180 mg/L 181 mg/L

The level of total hardness in water can be evaluated with commercial testing kits, which measure the concentrations of calcium and magnesium. Several scales are used to describe the hardness of water in different contexts. The hardness is indicated by a calculation where both calcium and magnesium values are reported as mg/L (ppm) (Ca x 2.5) + (Mg x 4.12)= Hardness in mg/L

E. Chemicals and Equipments

CaCO3 Aquadest HCL 6M Na-EDTA Buffer Solution PH 10 BET Indicator Volumetric Flask 100 mL Conical flask 100 mL Graduated Cylinder 10 mL Burette Volumetric Pipette Pipette Mineral water

F. Procedure Standardization of Na-EDTA with CaCO3 as primery standard

0,0804 grams of CaCO3 Moving to the volumetric flask 100 mL Adding aquadest 100 mL Adding HCl 1:1 drops by drops until bubbles gas lose Diluting until limit sign Shaking well CaCO3 as primery standardnCaCO3 Pipette 10 ml into conical flask Adding 5 ml buffer solution with pH 10 Adding 3 drops of EBT indicators Titrating with Na-EDTA 0,01 M Stop when there is changes color from red wine become blue Calculate concentration of Na-EDTA solution Ca2+ + Y4- CaY2-nCaCO3

Determining hardness of well Water

10 ml well water

Pipette into conical flask Adding 2 ml buffer pH 10 Adding 3 drops of EBT indicators Titrate wit Na-EDTA standard until limit sign Calculate hardness of CaCO3/ liter

Ca + Y CaY nCaCO3

2+

4-

2-

G. Experimental Data
Standardization of Na-EDTA with CaCO3 as primery standard

No
1

Procedure

Experiment Hypothesis Result

o CaCO3 white o CaCO3
solution +

/ Reaction
=
o Before

Conclusion
M of Nais

0,0804 grams of CaCO3 Moving to the volumetric flask 100 mL Adding aquadest 100 mL Adding HCl 1:1 drops by drops until bubbles gas lose Diluting until limit sign Shaking well CaCO3 as primery standard Pipette 10 ml into conical flask Adding 5 ml buffer solution with pH 10 Adding 3 drops of EBT indicators Titrating with NaEDTA 0,01 M Stop when there is changes color from red wine become blue Calculate concentration of Na-EDTA solution Ca2+ + Y4- CaY2-

titrated

EDTA

H2O = turbid

CaCO3(s) + 2 0,0108 HCl(aq) CaCl2(aq) + H2O(l)+ CO2

o CaCO3
= colorless

+
(g) o Sample:

H2O + HCl

red

wine +
o

o CaCl2
Buffer solution colorless

After titrated with Na-

EDTA

Ca2+ + Y4+

o CaCl2
Buffer solution EBT indicator pink

CaY2-

o Titrated with
Na-EDTA= pink become blue

o V1Na-EDTA
= 7,3 ml

o V2
ml

Na-

EDTA = 7,4

o V3
ml

Na-

EDTA = 7,4

Determining Hardness of Well Water No 1 10 ml well water Pipette into conical flask Adding 2 ml buffer pH 10 Adding 3 drops of EBT indicators Titrate wit NaEDTA standard until limit sign Calculate hardness of CaCO3/ liter in well water Procedure Experiment Result V1= 7,3 ml V2 = 7,0 ml V3 = 7,1 ml Well water colorless Buffer solution colorless Well water + buffer + EBT red wine After titrated with EDTA solution Nablue Hypothesis/ Reaction Ca + Y CaY
2+ 4-

Conclusion Hardness of well is water 776,667

2-

ppm Well water from Widang (Tuban)

Ca + Y CaY

2+

4-

2-

H. Analysis and Discussion Analysis

a. Standardization Na-EDTA 0,01 M with CaCO3 as primery standard solution In our experiment, we use 0,0804 gram of 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 1:1 drops by drops until the bubbles lose (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 pure solution. After that we pipette 10 ml of CaCl2 solution 5ml of buffer solution. And we add 3 drops of EBT indicators. In the basic, this titration formed complex ions, Ca2+ with EDTA. The metals will form complex with EDTA in different pH. Ca2+ 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 (H3In). 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 wine. 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 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 was added to a solution containing Ca2+, CaY2- the more stable will be formed by free Mg2+ to react with the indicator (EBT) and form MgIn- red. After the calcium is used in full, additional titrant change MgInand MgY2 indicator turns into a blue HIn2-form. In this experiment we need NaEDTA 7,3 ml, 7,4 ml, and 7,4 ml.Then we calculate molarity of Na-EDTA by using formula mol Na-EDTA = mol CaCO3. The molarity of Na-EDTA that we get is 0,0110 M, 0,0108 M, 0,0108 M. Calculation : 1. Known : mass of CaCO3 = 0,0804 V Na-EDTA = 7,3x 10-3 L With metallic ion: Ca2+ so it become

Asked : M of Na-EDTA Answer: In the equivalent point Mol Na-EDTA MxV = mol CaCO3 =MxV x 0,01 L

M x 7,3 x 10-3 L = M = 0,0110 2. Known : mass of CaCO3 = 0,0804 Asked : M of Na-EDTA Answer: In the equivalent point Mol Na-EDTA MxV

V Na-EDTA = 7,4x 10-3 L

= mol CaCO3 =MxV x 0,01 L

M x 7,4 x 10-3 L = M = 0,0108 3. Known : mass of CaCO3 = 0,0804 Asked : M of Na-EDTA Answer: In the equivalent point Mol Na-EDTA MxV

V Na-EDTA = 7,4x 10-3 L

= mol CaCO3 =MxV x 0,01 L

M x 7,4 x 10-3 L = M = 0,0108 So the average Molarity of Na-EDTA is : = = 0,0108 M b. Determine hardness of well water

In here we use well water from Widang Tuban Jawa Timur, then we add 10mL, then we add 2 ml of buffere solution. The purpose of addition buffer solution is same with above experiment. And we use EBT indicator is also same with the reason above. The sample of our group is use the well water is from Widang, Tuban Jawa Timur. The calculation : 1. Known : V well water = 10 ml V Na-EDTA = 7,3 x 10-3 L

Asked Answer

: hardness of well water : we use formula in eqivalent point mol CaCO3 = Mol Na-EDTA MxV M x 0,01 L = MxV = 0,0108 M x 7,3 x 10-3 L

M = 0, 0079 n =MxV = 0,0079 x 0,01 L = 7,9 x 10-5 mol m = n x Mr = 7,9 x 10-5 mol x 100,09 = 0,0080 g = 8,0000 mg Hardness = = 800 ppm 2. Known : V well water = 10 ml V Na-EDTA = 7,0 x 10-3 L Asked Answer : hardness of well water : we use formula in eqivalent point mol CaCO3 = Mol Na-EDTA MxV M x 0,01 L = MxV = 0,0108 M x 7,0 x 10-3 L

M = 0, 0076 n =MxV = 0,0076 x 0,01 L = 7,6 x 10-5 mol m = n x Mr = 7,6 x 10-5 mol x 100,09 = 0,0076 g = 7,6 mg Hardness = = 760 ppm 3. Known : V well water = 10 ml

V Na-EDTA = 7,1 x 10-3 L Asked Answer : hardness of well water : we use formula in eqivalent point mol CaCO3 = Mol Na-EDTA MxV M x 0,01 L = MxV = 0,0108 M x 7,1 x 10-3 L

M = 0, 0077 n =MxV = 0,0077 x 0,01 L = 7,7 x 10-5 mol m = n x Mr = 7,7 x 10-5 mol x 100,09 = 0,0077 g = 7,7 mg Hardness = = 770 ppm Average of Well Water Hardness = = 776,6667 ppm So from our calculation we know that well water from Widang (Tuban) is very hardness. Because in Tuban there is lime mountain, and it can cause the hardness become too high.

Discussion
In our experiment, there are no mistake and our result is appropriate with the theory. I. Conclusion o o J. Molarity of Na-EDTA is 0,0108 M Hardness of well water is 776,667 ppm

Question Answer 1. Complexiometric Titration Chemical Formula of Na-EDTA

Molecular formula of Na-EDTA (HO2CCH2)2NCH2CH2N(CH2CO2H)2 Structure of EBT indicator

Its chemical formula can be written as HOC10H6N=NC10H4(OH)(NO2)SO3Na. 2. Solution cencentration CaCl2 by ppm Known : V well water = 10 ml V Na-EDTA = 7,3 x 10-3 L Asked Answer : hardness of well water : we use formula in eqivalent point mol CaCO3 = Mol Na-EDTA MxV M x 0,01 L M = MxV = 0,0108 M x 7,3 x 10-3 L = 0, 0079

n =MxV = 0,0079 x 0,01 L = 7,9 x 10-5 mol m = n x Mr = 7,9 x 10-5 mol x 100,09 = 0,0080 g = 8,0000 mg Hardness = = 800 ppm Known : V well water = 10 ml V Na-EDTA = 7,0 x 10-3 L Asked Answer : hardness of well water : we use formula in eqivalent point mol CaCO3 MxV = Mol Na-EDTA = MxV

M x 0,01 L M n =MxV

= 0,0108 M x 7,0 x 10-3 L = 0, 0076

= 0,0076 x 0,01 L = 7,6 x 10-5 mol m = n x Mr = 7,6 x 10-5 mol x 100,09 = 0,0076 g = 7,6 mg Hardness = = 760 ppm Known : V well water = 10 ml V Na-EDTA = 7,1 x 10-3 L Asked Answer : hardness of well water : we use formula in eqivalent point mol CaCO3 = Mol Na-EDTA MxV M x 0,01 L = MxV = 0,0108 M x 7,1 x 10-3 L

M = 0, 0077 n =MxV = 0,0077 x 0,01 L = 7,7 x 10-5 mol m = n x Mr = 7,7 x 10-5 mol x 100,09 = 0,0077 g = 7,7 mg Hardness = = 770 ppm 3. NH4OH + NH4Cl buffer [OH-] = =

k b [ Base ] [ Salt ]
kb [ NH 4OH ] [ NH 4 ]

= pH 10 pOH pOH 4

1,8 x 105 x [ NH 4OH ] [ NH 4 ]

= 14 pOH = 14 pOH = 4 = - log [OH-] = - log [OH-]

[OH-] = 10-4

10-4

1,8 x 105 x [ NH 4OH ] [ NH 4 ]

1,8 x 10 5 10 4

[ NH 4OH ] [ NH 4 ]
[ NH 4OH ]

mass molecularmass . V
mass 35 . V

1,8 x 10-5

6,3 x 10-4 . V = gr eq VNH4OH so mass

[ NH 4OH ]
[ NH 4 ]

= 1L = 6,3 x 10-4 gram =

mass molecularmass . V
mass molecularmass . V

4.

Since the perfection of the reaction depends on the pH titration titrant, the higher the pH the better, so that the required buffer solution. (V1 V2) EDTA = 15,28-10,43 = 4,85 mL

5.

Known

VEDTA 1= 15,28 mL MEDTA = 0,01016 M VEDTA 2= 10,43 mL

Question Answer

: :

ppm CaCO3 dan ppm MgCO3 ?

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 ppm CaCO3 = = ppm MgCO3 mmol MgCO3 = = = = mmol EDTA [ M x (V1 V2)] EDTA 0,01016 x 4,85 0,0493 mmol
10 ,59 mg 0,1 L

105,9 mg/L

mg MgCO3 = mmol x Mr = 0,0493 x 84 = 4,1412 mg ppm MgCO3 = =

4,1412 mg 0,1 L
41,412 mg/L

K. References
Eriochrome Black T - Wikipedia, the free encyclopedia.html Day,R.A.,Underwood,A.L.(1991).Quantitative Prentice Hall. Tim Penyusun.(2011).Panduan Praktikum Kimia Analitik 1 Dasar-dasar Kimia Analitik.Surabaya:Jurusan Kimia FMIPA UNESA. Titrasi Pengomplekan Meilina Rizky Hadiyanti.html Rehma Standardisasi Larutan Na-EDTA 0,01 M dengan CaCl2 Sebagai Baku dan Aplikasinya dalam Penentuan Kadar Kesadahan Air Laut..html Analysis (Sixth ed).New York:

L. Attachment
Standardization Na-EDTA with CaCO3 as primery standard After titration Titrator

Istiana Yuli Purwati

Nurhalimah

Romadhoni

Determining Hardness of Well Water

Picture Before Titration After Titration

Titrator

Romadhoni

Istiana

Nurhalimah