Determination of Total Hardness as PPM CaCO3

Objectives
Standardize

EDTA solution

Determine

the hardness of any given sample as CaCO3

Introduction

Complexiometry
Complex-formation
A

reactions

complex is a molecule or ion formed by the reaction of two or more ions or molecules capable of independent existence.
metal

ion in solution and a complexing agent

Introduction

Water hardness is measured by the amount of minerals dissolved in water.

Hard water
Better water when

for health reacts with soap to produce soap curd

heated, soap curd is formed, which clogs pipes and industrial boilers

Calcium concentrations up to and exceeding 100 mg/l are common in natural sources of water, particularly groundwater.
SOFT WATER Slightly Hard Water Moderately Hard Water Hard Water Very Hard Water 0-1 GRAINS PER GALLON 1-31/2 Grains per Gallon 31/2-7 Grains per Gallon 7-101/2 Grains per Gallon Over 101/2 Grains per Gallon 1 grain/gallon = 17.13761522325 ppm

Introduction
EDTA

(Ethylenediaminetetraacetic acid)

chelating

agent -a substance whose molecules can form several bonds to a single metal ion. (In other words, a multidentate ligand.) ligand
used in soaps and detergent

hexadentate
often used

to determine the amount of calcium in water

Introduction
Eriochrome
azo

Black T indicator
indicator

complexometric

dye

In-Ca(aq)

(RED) -> In2- (BLUE) + Ca2+

Procedure

Preparation of Ammonia Buffer

0.64 g NH4Cl
5.7 mL conc. NH3

Dilute to 100 mL

Preparation of EBT Indicator

Dissolve 0.25 g Eriochrome Black T in 50 mL ethanol.

Preparation of EDTA Solution

225 mL H2O

0.5 g EDTA

0.25 g NaOH 0.025 g MgCl2

And then dilute to 250 mL in a volumetric flask.

Preparation of CaCO3 Solution 5 mL conc. HCl O.1 0.15 g CaCO3

5 mL H20 rinsing down sides of the beaker

250 mL beaker

Boil 5 minutes to remove CO2

Dilute to 250 with distilled H2O in a volumetric flask.

So now we have:

100 mL ammonia buffer

50 mL EBT solution

250 mL EDTA solution

250 mL CaCO3 solution

indicator

titrant

25 mL

100 mL ammonia buffer

250 mL CaCO3 solution

250 mL Erlenmeyer flasks

10 mL

100 mL ammonia buffer

Check if pH is 10. If not, add conc. NH3 dropwise. A B C

250 mL Erlenmeyer flasks

2 drops EBT

Titrate!

A, B, C

Analysis of Unknown

25 mL sample

Dilute to to 100 mL

Pipet 10 mL into 100 mL vol. flask

Check if pH = 10

Titrate!

Questions

What is the purpose of the Ammonia Buffer?

Effect of pH on EDTA: The most basic form (Y4-) of EDTA is that which reacts with metal ions, forming a 1:1 complex At high pH, the concentration of of Y4- is very low.

Y 4

[Y 4 ] [H6Y 2 ] [H5Y ] [H 4Y ] [H 3Y ] [H 2Y 2 ] [HY 3 ] [Y 4 ]

Y 4
Y 4

[Y 4 ] EDTA
{[H ]6 [H ]5 K1 [H ] 4 K1K 2 [H ]3 K1K 2 K 3 [H ]2 K1K 2 K 3 K 4 [H ]K1K 2 K 3 K 4 K5 K1K 2 K 3 K 4 K 5 K6 } K1K 2 K 3 K 4 K5 K6

*war flashbacks*

Effect of pH on metal ions: The higher the formation constant of the ligand, the lower the minimum pH needed for titration.

Why add NaOH to EDTA solution?

EDTA

is essentially insoluble in water, and will only dissolve when neutralized with sodium hydroxide to a pH = 8.0.

Why is HCl added to the CaCO3 Solution?

Calcium

carbonate reacts with hydrochloric acid to produce calcium chloride and carbonic acid, which then, dissociates into Ca2+, Cl2-, CO2 and water. It liberates the calcium ion. CaCO3(s) + 2 H3O+(aq) 2 Cl-(aq) ----> Ca2+(aq) + CO2(aq) + 3 H2O(l) + 2 Cl-(aq)

Why do we slowly add water to the sides of the beaker containing conc. HCl?

A large amount of heat is released when strong acids are mixed with water. If you add water to acid, you form an extremely concentrated solution of acid initially. So much heat is released that the solution may boil very violently, splashing concentrated acid out of the container.

What is the role of MgCl2 in the experiment?

End point will be sharper if MgCl2 is added.
very science

wuch wow

CASE 1: Without MgCl2

(colorless)

HIn2-(aq) + Ca2+(aq) CaHIn(aq) Ca2+ Before Kf = 2.5 x 105titration

CaHIn
(wine red)

CASE 1: Without MgCl2

Y4-(aq) + CaHIn Kf (wine red)

Ca2+
(colorless)

Y4- added. Reacts with free Ca2+(aq) CaY2-(aq) calcium ions. = 5.0 x 1010

[CaY]2(colorless)

During titration

CASE 1: Without MgCl2

CaHIn
(wine red)

Y4- has reacted with all free calcium ions.

[CaY]2(colorless)

Before equivalence point

CASE 1: Without MgCl2

(blue)

HIn2-CaHIn + Y4-

CaHIn
(wine red)

[CaY]2(colorless)

Y4- reacts with the calcium that is complexed with indicator. Free 2CaY2- + HIn indicator ion is blue, forming a purple color when mixed with wine-red.

Before equivalence point

CASE 1: Without MgCl2

HIn2(blue)

As Y4- is added, [CaHIn] decreases, [HIn2-] increases, making the solution more blue than red.

CaHIn
(wine red)

[CaY]2(colorless)

Before equivalence point

CASE 1: Without MgCl2

HIn2(blue)

At equivalence point

[CaY] 2(colorless)

CASE 2: With MgCl2

Ca

2+

Before titration

(colorless)

CaHIn
(wine red)

CASE 2: With MgCl2

CaHIn

(wine red) (wine-red) Mg2+ + CaHIn

Y4- added. Mg2+ in 2- is 422[MgY] CaHIn + Y CaY + HIn displaced 2+ 222+ Ca + MgY CaY + Mg MgHIn by Ca2+.

Ca2+

Mg2+

MgHIn + Ca2+

(colorless) (colorless)

[CaY]2(colorless)

During titration

CASE 2: With MgCl2

Y4- added. All Ca2+ is consumed

CaHIn

MgHIn

(wine red) (wine-red)

[CaY]2-

Mg2+
During titration

(colorless) (colorless)

CASE 2: With MgCl2

Y4- added. All Mg2+ is consumed.

CaHIn

MgHIn

(wine red) (wine-red)

[CaY]2- [MgY]2(colorless) (colorless)

Before equivalence point

CASE 2: With MgCl2

CaHIn

Mg2+ + Y4- MgHIn

Y4displaces HIn2- in CaHIn. 2MgY

(wine red) (wine-red)

[CaY]2- [MgY]2(colorless) (colorless)

HIn2(blue)

Before equivalence point

CASE 2: With MgCl2

[CaY]2-

4- MgY2- + Hin 2MgHIn + Y [MgY]

Y4displaces HIn2- in MgHIn. 2-

(colorless) (colorless)

HIn2(blue)

Equivalence point

See the difference? No? Lets look at them side-by-side:

See the difference? No? Lets look at them side-by-side:

See the difference? No? Lets look at them side-by-side:

See the difference? No? Lets look at them side-by-side:

See the difference? No? Lets look at them side-by-side:

See the difference? No? Lets look at them side-by-side:

Results
Things
1

to remember:
is supposedly insignificant relative to

mol Eriochrome Black T = 1 mol CaCO3

[Mg2+]

[Ca2+].

Weight MgCl2.6H2O = 0.025g FW MgCl2.6H2O = 112.533g/mol

molMgCl2.6H20= 2.22 x 10-4 mol

Diluted to 250 mL 8.88x10-4 M

Weight CaCO3 = 0.1-0.15 g FW CaCO3 = 100g/mol molCaCO3= 1.0x10-3-1.5x10-3 Diluted to 250 mL 4.0x10-3 - 6.0x10-3 M

Results - Standardization
Weight of CaCO3: 0.1410 g

Equation:
MEDTA = [(MCaCO3)(VCaCO3)]/VEDTA Sample Computation: ={ {(0.1410g)/[(100moles/g)(0.025L)]} * 0.025L } / 0.0222 = 0.0635 M

Results-Standardization
Trial 1 2 3 Volume of EDTA (mL) 22.2 22.2 22.4 Molarity of EDTA 0.0635 0.0635 0.0629 0.0633

Results Analysis of the Unknown

Trial 1 2 Volume of water sample (mL) 10 10 Volume of EDTA (mL) 21.5 21.6 Total hardness (ppm CaCO3) 13609.5 13672.8 13609.5

10

21.5

13630.6

Results Analysis of the Unknown

molCaCO3 = molEDTA

ppm CaCO3 = mg CaCO3 / Lsample

= {[0.0633mol/L)(0.0215L)]/100000mg/mol}/0.01L = 13609.5 ppm

Results-Analysis of the Unknown

SOFT WATER 0-1 GRAINS PER GALLON

Slightly Hard Water

Moderately Hard Water Hard Water Very Hard Water

1-31/2 Grains per Gallon

31/2-7 Grains per Gallon 7-101/2 Grains per Gallon Over 101/2 Grains per Gallon

13609.5 ppm 17.14 ppm 1 grain/gallon = 794.02 grain/gallon

1 grain/gallon = 17.13761522325 ppm

Sources

http://www.uclmail.net/users/dn.cash/EDTA2.pdf http://www.thewaterclinic.com/info-hardness.php http://www.elmhurst.edu/~chm/vchembook/554soap.html http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Descriptive_Chemistry/Ma in_Group_Elements/Main_Group_Reactions/Case_Study%3A_Hard_Water http://scifun.chem.wisc.edu/chemweek/chelates/chelates.html http://chemwiki.ucdavis.edu/Inorganic_Chemistry/Coordination_Chemistry/L igands http://www.chem.purdue.edu/gchelp/cchem/whatis.html