Objec&ve

Apply the concept of complexometric titration in the

determination of total hardness in drinking water

Simple Water and Complexes

Water
Drinking
Hard water is better for
drinking because it
contains minerals

Water
Cleaning
Soft water is better for
cleaning because it
doesnt form scum with
soap

Water
Hardness of water
Depends on source
Caused by Ca2+ and
Mg2+ forming
precipitates with soap

Water
Hardness of water
Most Ca2+ in water
come from CaCO3
exoskeletons of aquatic
microorganisms like
diatoms

Complexes
Coordination between

metal and ligand

An atom in the ligand

(called the donor)

donates electrons to the
metal ion, forming a
bond.

New properties
Complexes are usually
more stable than the
components due to the
rearrangement of the
energy levels of the dorbital (crystal field
theory)

Complexes - Ligands
Monodentate
Polydentate
Chelating agents Gr.
chelos, meaning teeth

Polyanionic
Complex-forming
Reacts in a 1:1 ratio

Complexes - Usage
Catalysts
Polymerization, hydrogenation, hydroboration, etc.
Medicine
cis-diamminedichloroplatinum(II)
NH3
Cl
Chelators
Heavy Metal Poisoning Treatment
Pt
Cleaning agent
Food enhancement
NH3
Cl
Anti-b acterial
Titrants

Step by step discussion

*simple dilutions are not discussed

Solu&on Prepara&on

Solu&on Prepara&on
250 mL 0.050 M std CaCO3soln
1.2511 g CaCO3
standard

+ 20 mL dH2O, +few
drops 6M HCl
(Dissolve precipitate,
basic CO32-)

Rinse watch glass to

beaker

Cover with watch

glass (slower
evaporation rate to
keep beaker from
getting dry)
Evaporate to 10 mL.
Cool.

Quantitatively transfer to 250 mL vol flask. Dilute to mark.

Solu&on Prepara&on
pH 10 buffer
142 mL conc NH3 +
17.5 g NH4Cl

Adjust soln to pH 10

Transfer to 250 mL
vol flask. Dilute to
mark.

pOH = pKb + log([ NH 4+ ] /[ NH 3 ])

pOH = log(1.8 x10 5 ) + log(2.1016mol / 0.327mol )
pOH = 4.74 + 0.808
pH = 8.45
Add ammonia to increase pH!

Solu&on Prepara&on
pH 10 buffer
142 mL conc NH3 +
17.5 g NH4Cl

Adjust soln to pH 10

Transfer to 250 mL
vol flask. Dilute to
mark.

Different minimum pH values for different cations

Mn2+, Fe2+, 5-6 pH
Fe3+, Th4+ 1-1.5 pH
Ca2+ 8
Mg2+ 10

Solu&on Prepara&on
pH 10 buffer
142 mL conc NH3 +
17.5 g NH4Cl

Adjust soln to pH 10

Transfer to 250 mL
vol flask. Dilute to
mark.

As a rule of thumb,
The higher the pH (more basic solution), the sharper
the endpoint
The higher the formation of constant the lower the
minimum pH

Solu&on Prepara&on
500 mL 0.050 M EDTA
9.31 g Na2H2EDTA2H2O

+200 mL dH2O

+1.0 g
MgCl26H2O

Dissolve in 500 mL vol

flask. Heat if necessary.

Solu&on Prepara&on
500 mL 0.050 M EDTA

Why add 1.0 g MgCl26H2O?

Diverse ion effect: increase solubility (easier

preparation)
Sharper endpoint in titration

Ensures presence of Mg2+ in sample

Supposedly does not affect titration procedure

What exactly happens when we add MgCl2?

Good question.

Solu&on Prepara&on
500 mL 0.050 M EDTA
What happens when we DONT add MgCl2?
Endpoint not as sharp if Mg2+ is not present in solution
Only total hardness can be computed (Ca2+ and Mg2+)
HO

O
S

O
O
N

Mg

Figure 1. Structure of eriochrome black T magnesium complex

Eriochrome Black T
EBT is blue in a buffered
solution at pH 10. It turns
red when Ca2+ ions are
added.
In its protonated form,
Eriochrome Black T is blue. It
turns red when it forms a
complex with calcium,
magnesium, or other metal
ions.

Standardiza&on

http://xkcd.com/927/

Standardiza&on
10.00m L 0.0050 M wrk
std CaCO3

+ 3 mL buffer
+ 6 drps EBT

Reactions: (Consider w/o MgCl2)

Start:

Ca2+ + HIn2- CaHIn (Kf = 2.5x105)

Before equivalence point:

Ca2+ + H2Y2- CaH2Y(Kf = 5.0x1010)
At the end point:

CaHIn + Y2- CaH2Y + HIn2-

Titrate to blue
endpoint

Standardiza&on
w/o MgCl2
Ca2+ + HIn2-
CaHIn

Ca2+ + H2Y2- CaH2Y

CaHIn + Y2- CaH2Y + HIn2-

Standardiza&on
10.00 mL 0.0050 M wrk
std CaCO3

+ 3 mL buffer
+ 6 drps EBT

Titrate to blue
endpoint

Reactions: (Consider w/ MgCl2)

Start:

Ca2+ + HIn2- CaHIn (Kf = 2.5x105)

Calcium-EBT complexation

Before equivalence point:

Ca2+ + H2Y2- CaH2Y(Kf = 5.0x1010)

Calcium consumption
Ca2+ + MgH2Y CaH2Y + Mg2+
Magnesium Displacement
Mg2+ + CaHIn MgHIn + Ca2+
Magnesium-EBT complexation

Near the endpoint: Assume all Ca2+ consumed

Mg2+ + H2Y2- MgH2Y

Released Magnesium consumption

At the end point:

MgHIn + H2Y2- MgH2Y + HIn2-

Magnesium Displacement

Standardiza&on
w/ MgCl2
Ca2+ + HIn2-
CaHIn

Ca2+ + H2Y2- CaH2Y

Ca2+ + MgH2Y CaH2Y + Mg2+
Mg2+ + CaHIn MgHIn + Ca2+

Mg2+ + H2Y2- MgH2Y

MgHIn + H2Y2- MgH2Y + HIn2-

Standardiza&on
w/ MgCl2
Amount of EDTA corresponding to
Free EDTA to titrate released Mg2+

Amount of EDTA to titrate Ca2+

Amount of EDTA to
titrate Mg2+ in
indicator (negligible)

Standardiza&on
The amount of MgCl2 that was supposed to be

added was not in significant (0.0049 mol, compared

to EDTA that has 0.025 mol)

The addition of MgCl2 should be stoichiometric (Y=X)

or negligible (Y0) to EDTA in order for the titration to

be unaffected

Sample Analysis

Sample Analysis
50 mL
Viva

+ 3 mL buffer
+ 6 drps EBT

Titrate to blue
endpoint

Reactions: (Consider w/o MgCl2)

Start:

Mg2+ + HIn2- MgHIn (Kf = 1.0x107) Magnesium-EBT complexation

Before equivalence point:

Ca2+ + H2Y2- CaH2Y(Kf = 5.0x1010)

Calcium consumption

Near the endpoint: Assume all Ca2+ consumed

Mg2++H2Y2-MgH2Y(Kf=4.9x108) Present Magnesium consumption

At the end point:

MgHIn + H2Y2- MgH2Y + HIn2-

Magnesium Displacement

Sample Analysis
w/o MgCl2
Mg2+

HIn2-

MgHIn

Ca2+ + H2Y2- CaH2Y

Mg2+ + H2Y2- MgH2Y

CaHIn + Y2- CaH2Y + HIn2-

Sample Analysis
50 mL
Viva

+ 3 mL buffer
+ 6 drps EBT

Titrate to blue
endpoint

Reactions: (Consider w/ MgCl2)

Start:

Mg2+ + HIn2- MgHIn (Kf = 1.0x107) Magnesium-EBT complexation

Before equivalence point:

Ca2+ + H2Y2- CaH2Y(Kf = 5.0x1010)
Ca2+ + MgH2Y CaH2Y + Mg2+

Calcium consumption
Magnesium release

Near the endpoint: Assume all Ca2+ consumed

Mg2++H2Y2-MgH2Y(Kf=4.9x108) Present Magnesium consumption
Released Magnesium consumption
At the end point:
MgHIn + H2Y2- MgH2Y + HIn2-

Magnesium Displacement

Sample Analysis
w/ MgCl2
Mg2+ + HIn2- MgHIn

Ca2+ + H2Y2- CaH2Y

Ca2+ + MgH2Y CaH2Y + Mg2+

Mg2+ + H2Y2- MgH2Y

MgHIn + H2Y2- MgH2Y + HIn2-

Sample Analysis
w/ MgCl2
Amount of EDTA corresponding to
Free EDTA to titrate released and present Mg2+

Amount of EDTA to titrate Ca2+

Amount of EDTA to
titrate Mg2+ in
indicator (negligible)

Sample Analysis
w/ MgCl2
Y

Amount of EDTA to
titrate Mg2+ in
indicator (negligible)

Sample Analysis
w/ MgCl2

Let X =
Y=

Sample Analysis
w/ MgCl2

Let X =
Y=

Sample Analysis
The amount of MgCl2 that was supposed to be

added was significant (0.0049 mol, compared to

EDTA that has 0.025 mol)
The addition of MgCl2 should be negligible
(EDTA:Mg0) with respect to EDTA in order for the
titration to be unaffected

Sample Analysis
Back Titration with EDTA is possible
Add standardized amount of EDTA
Back titrate with Mg2+

Molarity of Primary Standard

Weight 1o std: 1.2511 g
%Purity 1o std: 99.9%
Final volume std: 250 mL
Vol std sol'n: 5 mL
Final vol working std: 50 mL

Molarity of Primary Standard

The molarity of the working standard can be

computed from the given

Volume of &trant used in

standardiza&on
Volume
working std
CaCO3
Final volume
Initial
volume
Net volume

Trial 1

Trial 2

Trial 3

10

10

10

14.1

28

41.8

0.4

14.1

28

13.7

13.9

13.8

Molarity of EDTA
Volume
Net volume
wrking std
EDTA
Std A
10 mL
13.7 mL
Molarity:

Molarity

Titer of EDTA
nEDTA =
Molarity
nCaCO3
Std A 0.003646 M
1
Titer:

Titer

Total Hardness of Viva

Volume of
Total
Water
Vol EDTA Amount of
Sample
Calcium
Sample A
50 mL
19.5 mL

Total Amount of Calcium:

Total hardness in ppm CaCO3:

Total hardness in ppm

CaCO3

Collec&ve Data
Team
1

Group
1
2
3

Trial1
142.58

Trial2
142.58

Trial3
139.02

Average
141.40

140.61

139.89

140.61

4
5
6

148.57
151.40
141.29

149.32
140.83
142.02

147.83
140.13
144.92

7
8
9
10

148.38

138.63

136.54

140.37
140.88
148.57
144.12
142.74
145.14
141.19

139.15

142.66

138.45

Team Mean
2
Team Mean
3
Team Mean

140.09
140.64

Mean
Stdev
RSD

142.64
4.73
33.2

To Viva or not to Viva, that is the question

PPM Viva
Total hardness of 192.49 ppm CaCO3

Conclusion
25.8% difference between the mean and the claimed

value
Vivas water is softer than they claim it to be

References
J. Roger Hart; J. Chem. Educ., 1984, 61 (12), p 1060.
Blitz, Jonathan P. COMPLEXOMETRIC DETERMINATION OF Mg2+ and Ca2+. 2010. 25 January

2012 <http://www.ux1.eiu.edu/~cfjpb/teaching/quant/labs/experiment8.pdf>.
Garrett, Simon J. CEM 333 EDTA Formation Constants. 1998. 25 January 2012 <http://
www.cem.msu.edu/~cem333/EDTATable.html>.
Jackson School of Geosciences. COORDINATION CHEMISTRY. n.d. 25 January 2012 <http://
www.geo.utexas.edu/courses/376m/coord_chem.htm>.
Jon A. McCleverty, Thomas J. Meyer. "Applications of Coordination Complexes." 2003. Platinum
Metals Review. 25 January 2012 <http://www.platinummetalsreview.com/pdf/101-104-pmrjul04.pdf>.
Mccord, Dr. Stephen P. Determination of Water Hardness using Complexometric titration. 2005. 25
January 2012 <http://mccord.cm.utexas.edu/courses/spring2005/ch455/Spr05455Wk4Lab.pdf>.
Old Dominion University. Chapter 12: EDTA Titrations. n.d. 25 January 2012 <http://www.odu.edu/
sci/xu/chem321/chem321chapter12.pdf>.
Prince George's Community College. ANALYSIS OF CALCIUM BY EDTA TITRATION TO ASSESS
WATER . n.d. 25 January 2012 <http://academic.pgcc.edu/psc/chm103/EDTA_Ca.pdf>.
Reckhow Research Group. CHAPTER XVI VOLUMETRIC METHODS. 17 June 2011. 25 January
2012 <http://www.ecs.umass.edu/cee/reckhow/courses/572/572bk16/572BK16.html>.
Sinex, Scott A. EDTA - A Molecule with a Complex Story. 1 August 2007. 25 January 2012 <http://
www.chm.bris.ac.uk/motm/edta/edtah.htm>.
UC Davis Department of Chemistry. EDTA TITRATIONS. 31 March 2004. 25 January 2012 <http://
www-chem.ucdavis.edu/2C/Old/06EDTA.pdf >.

He who asks is a fool for five minutes, but he who

does not ask remains a fool forever.