Determination of Total Hardness as

Parts-per-Million Calcium Carbonate

Elysse S. Salindo
Kyle Lendl N. Wong

Objectives

Standardize EDTA Solution

Determine hardness of any given sample
as CaCO3

Introduction

WATER

Is highly polar
Called the universal solvent
Can dissolve more substances than any
other known liquid
Natural water contains dissolved
substances usually from mineral deposits

Introduction

TOTAL WATER HARDNESS

Defined as the concentration of of

dissolved cations (particularly Ca2+ and
Mg2+) in a water sample
Can be expressed in ppm CaCO3,
grains per gallon, mmol/L, etc
A scale is given to describe how hard a
water sample is.

Introduction

Introduction

Two types of water hardness

Temporary hardness

Due to bicarbonate (HCO3-) present in

water
Can be removed by boiling the water to
expel CO2

Permanent hardness

due to the presence of the ions Ca2+, Mg+2,

Fe3+ and SO4-

Cannot be eliminated by boiling

Introduction

HARD WATER

Is a nuisance
Precipitation of calcium carbonate is
endothermic so when hard water is
heated, it forms solid CaCO3

Water pipes, boilers, tea kettle, etc.

Reduce effectiveness of soap

Interacts with soap and forms an insoluble
soap scum

Very difficult to clean

Introduction

Introduction

COMPLEXOMETRIC TITRATION

Reaction that involves the binding of metal

ions with a ligand/complexing agent
Solution containing metal ion of interest
(water sample) is titrated with a solution of
chelating agent (EDTA)
Endpoint is determined with an indicator
(EBT) capable of forming a colored
complex with the metal ion

Introduction

Ethylenediamminetetraacetic acid (EDTA)

Hexadentate ligand
Tetrabasic or fully deprotonated
form (Y4-) can form at most 6 bonds
to a single metal ion
Forms 1:1 complex with metal ions
regardless of charge
Effectiveness (as a ligand) depends
on pH level

Introduction

Eriochrome Black T Indicator (EBT)

Can form colored complex with metal ion

albeit less stable than EDTA-metal complex

When chelated (bonded to metal ion) =

wine-red in color

When not chelated = blue in color

Eriochrome Black T

Results

Standardization of EDTA

Weight of CaCO3 = 0.1169 g

Table1. Molarity of EDTA from Standardization with CaCO3

Trial

Volume of EDTA (mL)

Molarity of EDTA (M)

25.60

4.562 x 10-3

23.80

4.907 x 10-3

23.80

4.907 x 10-3

23.90

4.887 x 10-3

Average Molarity of EDTA = 4.816 x 10 -3

Results

Sample Computation:

MEDTAVEDTA = MCaCO3VCaCO3
M (25.60 mL) = ((.1169 g CaCO3)(100.09
EDTA

g/mol CaCO3) / .250 L ) (25mL CaCO3)

MEDTA= 4.562 x 10

-3

Results

Analysis of Unknown
Table 2. Total Hardness of Unknown Water Sample by Titration with EDTA

Trial

Volume of
water sample
(mL)

Volume of
EDTA (mL)

Total hardness
(ppm CaCO3)

10.00

26.80

1292

10.00

25.90

1248

10.00

25.60

1234

Average Total Hardness of sample = 1258 ppm

Results

Sample Computation:
MEDTAVEDTA = MunknownVunknown
-3

(4.816 x 10 M EDTA)(.02680 L EDTA) =

Munknown(.0100L unknown)
Munknown = 0.0129042
Hardness of water= (100.09 g/mol
CaCO3)(1000mg/1g)(.0129042 mol/L)
= 1292 mg/L
= 1292 ppm

Reactions Involved
Standardization of EDTA Solution:
4-

+ Ca

2+

CaY

2-

+ 2H+

Analysis of the Unknown:

Ca

2+

+ HIn

2-

(blue) CaIn (red) + H+

CaIn- (red) + Y4- CaY2- + Hin2- (blue)

Discussion

EDTA
2 Has many forms depending on pH conditions: H4Y, H3Y , H2Y ,
HY3- or Y4 Too low or too high pH can decrease the effectiveness of
EDTA as a ligand
pH,; EDTA is not fully deprotonated
pH; hydroxides will interfere with complexation by
bonding with Ca or Mg to form insoluble compounds.
Every ligand and metal ion complex has an optimum pH
Will depend on pKa of ligand and formation constant of
complex

Discussion

Discussion

Titrant was prepared by combining NaOH,

MgCl26H20 and EDTA.

NaOH was added to deprotonate EDTA so it is in

the form of Y4-

Mg2+ forms a complex with EDTA (prior to titration)

CaCO3 dissolved in concentrated HCl, water and

ammonia buffer then added EBT

Ca2+ forms a complex with EBT (causing the winered color of solution)

Discussion

PRIOR to titration

DURING titration

Analyte is wine-red in color due to the EBTmetal ion complex formed

Analyte gradually turns purple

AFTER titration/AT end point

Analyte is blue in color due to unchelated

EBT

Discussion

Discussion
At pH 10, HIn2- and Mg2+ form a red
complex.
Mg2+ + Hin2- (blue) MgIn- (red) +
H+
EDTA forms a weaker complex with
Mg2+ than Ca2+. Ca2+ reacts with Y4first, leaving the red MgIn- solution
Ca2+ + MgIn- (red) + Y-4 CaY-2 +
MgIn- (red)

Discussion
When all the Ca2+ is titrated by Y4-,
MgIn- reacts with Y4MgIn- (red) + Y4- MgY2- + In3(orane)
In-3 hydrolyzes
In3- (colorless) + H2O Hin2(blue) + OH-

Discussion

Prior to Titration
Mg-EDTA complex formed in the buret
Ca-EBT complex formed in the flask (wine-red color)

During Titration

Formation constants: Ca-EDTA > Mg-EDTA > Mg-EBT > Ca-EBT

Displacement Reaction: Ca-EBT Ca-EDTA and Mg-EDTA
Mg-EBT (nag-switch sila)

After Titration
EDTA chelates all Ca and Mg in solution thus leaving EBT
unchelated so analyte turns blue in color.

Conclusion and
Recommendation

Based on the scale for water hardness, the sample is

considered to be a very hard water
It is important to get as close as possible to the optimum
pH for a more successful and accurate titration
Exercise utmost care when quantitatively transferring
solutions (especially the standard)
Be very alert during titration especially near the end point
because even a small drop of excess can have huge
effects on the result