UNIVERSITY OF DAR ES SALAM

COLLEGE OF NATURAL AND APPLIED SCIENCE

(CoNAS)

CHEMISTRY DEPARTMENT

CH 241: CHEMISTRY PRACTICAL III

PHYSICAL CHEMISTRY PRACTICAL

PRACTICAL No: 2.60

PRACTICAL NAME: THE DISSOCIATION CONSTANT OF MAGNESIUM-EDTA

COMPLEX

PARTICIPANTS:

STUDENTS NAME REGISTRATION NUMBER

RASHIDI SHADIA KAUMBYA 2019-04-10947
KIMANI CRYSPIAN JOHN 2019-04-04189
DATE OF EXPERIMENT: 7th APRIL 2021

DATE OF SUBMISSION: 21th MAY 2021

ABSTRCT

The aim of experiment was to determine the dissociation constant of the Magnesium - EDTA
complex. Experiment conducted by titrimetric method. EDTA initially titrated against 0.096 M
Sodium hydroxide, then EDTA added magnesium chloride and titrated against using 0.096 M
sodium hydroxide while pH recorded. pH recorded used to plot the graphs against volumes of
sodium hydroxide. From the graph constants obtained were used to calculate the dissociation
constant of the Magnesium - EDTA complex. The dissociation constant of the Magnesium - EDTA
complex was 2.989 × 10 -9.
THEORY

Dissociation constant of Magnesium an equilibrium constant that measure tendency of larger

compounds to separate reversibly into smaller components as when a complex compound to break
into smaller components of its compound. The dissociation constant specifies the tendency of the
substances to reversibly dissociate in a solution. Ethylenediaminetetraacetic acid (EDTA) is
amino-carboxylic acid used in determination of the dissociation constant of magnesium. EDTA
deprotonated form is a Lewis base with a six-bonding site, that is it form four negatively charged
carboxylate group and two tertiary amino groups to create six pairs of electrons to a metal ion to
bond on it.

EDTA before deprotonation occur EDTA after deprotonation occurs

The resulting metal liquid complex in which EDTA form cage like structure around a metal ion
is very stable. Actual coordination site of EDTA depends on the size of a metal ion, however all
metal EDTA complex have 1:1 stoichiometry.

The structure of EDTA when it is fully deprotonated and occupied by metal

EDTA(H4Y) is a weak acid that dissociate to in a solution as it dissociates differently with different
pH and different dissociation constant as shown below

H4Y ⇌ H+ + H3Y- K1 = [H+][ H3Y-]/[ H4Y]

H3Y- ⇌ H+ + H2Y2- K2 = [H+][ H2Y2-]/[ H3Y-]

H2Y2- ⇌ H+ + HY3- K3 = [H+][ HY3-]/[ H2Y2-]

HY3- ⇌ H+ + Y4- K4 = [H+][ Y4-]/[ HY3-]

The dissociation constant Magnesium - EDTA complex determined using di-deprotonated EDTA
substituted with a metal on two carboxylate groups, (M2H2Y). H2Y2- is titrated with NaOH and a
titration curve is plotted using the value of pH measured using a pH meter and volume of sodium
hydroxide. From the graph dissociation constant of the EDTA will be obtained as K 3 and K4 for
the two protons removal and sodium metal to bond on two carboxylate groups. When MgCl 2 is
introduced to EDTA in titration it establishes an equilibrium with EDTA and NaOH as shown
below

H2Y2- + Mg2+ + 2OH- ⇌ Mg2+ + 2H2O

K5 = [H+]2[ MgY2-] / [ H2Y2-][Mg2+]

The value of dissociation constant for magnesium-EDTA complex can be determined

experimentally using the titration results or from the equilibrium constants K 3, K4 and K5 from the
graph.

MgY2- ⇌ Mg2+ + Y4-

KMg2+ = [Mg2+] [Y4-] / [MgY2-]

KMg2+ = K3 × K4 × K5-1
EXPERIMENTAL PART

Apparatus used
1 pH meter with glass calomel electrode used to measure pH during titration
1 Magnetic stirrer used to ensure uniform mixture during titration process
1 Beaker 250 mL used to mix samples together during titration and for pH determination
1 Burette 50 mL used to keep Sodium hydroxide during titration
2 Pipettes 10 mL used to measure volume of EDTA and Magnesium Chloride before titration
1 Measuring cylinder 100 mL used to measure volume of water during sample mixing prior to
titration process
Tripod stand used to hold burette during titration

Reagents used
0.1M Ethylenediaminetetraacetic acid (EDTA), 1.0 M Magnesium chloride, (MgCl 2), 0.096 M
Sodium hydroxide, (NaOH) and Distilled water.

Experimental procedures
Titration of EDTA
10 mL of 0.1 M of EDTA placed into a 250 mL beaker and it’s pH measured, then 80 mL of water
added into a beaker containing EDTA and its pH measured again. A mixture titrated against 0.1
M Sodium hydroxide while the pH recorded after every addition of 1.0 mL of Sodium hydroxide
addition until there is a sharp pH change occurs, then titration continued until there is a second
sharp pH change.
Titration of EDTA containing Mg2+ ions in excess
10 mL of EDTA placed into a 250 mL beaker, followed by 80 mL of water and pH measured.
Then Magnesium chloride added and pH measured. Thereafter a mixture titrated against Sodium
hydroxide while pH recorded after every addition of 1.0 mL of sodium hydroxide until there is
sharp pH change.
DATA AND CALCULATION

Raw data
Concentration of sodium hydroxide = 0.1 M
Concentration of magnesium chloride = 1.0 M
Concentration of EDTA = 0.1 M

For the value of K3

pK3 = pH - log ( )

pH = log ( ) + pK3

Where by
a is the volume of sodium hydroxide for first sharp pH change
b is the volume of sodium hydroxide before first sharp pH change
From the graph a = 11 mL and the values of b and pH are extrapolated from the graph
respectively
When b = 1.4 pH= 5.5
.
log ( ) = log
.

log ( ) = log 0.1458

log ( ) = - 0.8362

From the graph equation

y = 1.0239x + 6.3021

Compare with pH = log ( ) + pK3

pK3 = 6.3021
From pK3 = - log K3
K3 = log -1 (-pK3)
K3 = log -1 (-6.3021)
K3 = 4.99 × 10 -7
For the value of K4

pK4 = pH - log ( )

pH = pK4 + log ( )

a is the volume of sodium hydroxide for first sharp pH change

b is the volume of sodium hydroxide before first sharp pH change
From the graph 2a = 22 mL and the values of b and pH are extrapolated from the graph
respectively
When b = 11.4 mL pH= 8.9
.
log ( ) = log
.

log ( ) = log 0.0377

log ( ) = - 1.4232

From the graph equation

y = 0.7152x + 9.9823

compare with pH = pK4 + log ( )

pK4 = 9.9823
But pK4 = - log K4
K4 = log -1 (-pK4)
K4 = log -1 (-9.9823)
K4 = 1.042 × 10 -10
For the value of pK5

pH = (pK5 – log [Mg2+] + log ( )

pH = pK5 – 0.5log [Mg2+] + 0.5 log ( )

Concentration of magnesium ion, ([Mg2+])
10 mL of 1 M Mg2+ placed in a solution mixture containing 70 mL of distilled water and 10 mL
of EDTA.
From dilution law
Number of moles before dilution = Number of moles after dilution
10 mL × 1 M = 90 mL × [Mg2+]

[Mg2+]=

[Mg2+]=0.1111 M

pH = pK5 – 0.5log 0.1111M + 0.5 log ( )

pH = pK5 – 0.5log 0.1111M + 0.5 log ( )

pH = pK5 + 0.4771 + 0.5 log ( )

2A is the volume of sodium hydroxide for sharp pH change
B is the volume of sodium hydroxide before sharp pH change
From the graph 2A = 21.00 mL and the values of B and pH are extrapolated from the graph
respectively
B = 2.4 mL and pH = 3.85
.
log ( ) = log ( )
.

log ( ) = log 0.1290

log ( ) = -0.8893

From the graph equation

y = 0.4919x × 4.3569

Comparing with pH = pK5 + 0.4771 + 0.5 log ( )

4.3569 = pK5 + 0.4771

pK5 = 4.3569 – 0.4771

pK5 = 3.8798

pK5 = 3.8798 × 2
pK5 = 7.7595
But pK5 = - log K5
K5 = log -1 (-pK5)
K5 = log -1 (-7.7595)
K5 = 1.7394 × 10 -8

For the dissociation constant of the Magnesium – EDTA complex

×
KMg2+ =

KMg2+ = (4.99 × 10 -7 × 1.042 × 10 -10) × (1.7394 × 10 -8)-1

KMg2+ = 2.989 × 10 -9
RESULTS

Table for values of pH, Volume of NaOH before sharp pH change, and log ( )

pH a (mL) b (mL) a – b (mL) ( ) (mL) log ( )

5.5 11.00 1.4 9.6 0.1458 -0.8362

6.1 11.00 4.6 6.4 0.7188 -0.1434
6.4 11.00 6.4 4.6 1.3913 0.1434
6.6 11.00 7.4 3.6 2.0556 0.3129
7.1 11.00 9.2 1.8 5.1111 0.7085

THE PLOT OF pH AGAINST log ( )

pH y = 1.0239x + 6.3021
R² = 0.99
8

0
-1 -0.8 -0.6 -0.4 -0.2 0 0.2 0.4 0.6 0.8

pK3 from the graph = 6.3021

K3 = 4.99 × 10 -7
Table for values of pH, Volume of NaOH before second sharp pH change, and log ( )

pH 2a (mL) b (mL) b - a (mL) 2a – b (mL) 𝑏−𝑎

log ( )
2𝑎 − 𝑏
8.9 22.00 11.4 0.4 10.6 0.0377 -1.4232
9.6 22.00 13.6 2.6 8.4 0.3095 -0.5093
9.8 22.00 14.6 3.6 7.4 0.4865 -0.3129
10.4 22.00 18.8 7.8 3.2 2.4375 0.3869
10.9 22.00 21.60 10.6 0.4 26.5 1.4232

THE PLOT OF pH AGAINST log ( )

y = 0.7152x + 9.9823
pH R² = 0.9846

12

10

0
-2 -1.5 -1 -0.5 0 0.5 1 1.5 2

pK4 from the graph = 9.9823

K4 = 1.042 × 10 -10
Table for values of pH, Volume of NaOH before sharp pH change, and log ( )

pH 2A (mL) B (mL) 2A – B (mL) B

log ( )
2A − B
3.85 21.00 2.40 18.60 0.1290 -0.8893
4.20 21.00 6.60 14.40 0.4583 -0.3388
4.40 21.00 10.6 10.40 1.0192 0.0008
4.65 21.00 15.4 05.60 2.7500 0.4393
5.05 21.00 20.4 00.60 34.0000 1.5315

THE PLOT OF pH AGAINST log ( )

y = 0.4919x + 4.3569
pH R² = 0.9802
6

0
-1.5 -1 -0.5 0 0.5 1 1.5 2

pK5 from the graph = 4.3569 and K5 = 1.7394 × 10 -8

The value of dissociation constant of the Magnesium – EDTA complex is

The dissociation constant of the magnesium – EDTA complex was 2.989 × 10 -9

DISCUSSION

The value of dissociation constant K3 (K3 = 4.99 × 10 -7) obtained is greater that dissociation
-10
constant K4, (K4 = 1.042 × 10 ). This means the first equivalent point show that H 2Y2- have
higher acidic strength therefore it readily ionizes to give HY3- and H+ during titration and second
equivalent point show that HY3- acidic strength decrease therefore, it ionizes the last proton weakly
to give Y4- and H+ during titration, hence K4 be smaller than K3, (K3 > K4).

The smaller value of K5, (1.7394 × 10 -8) than K3 means that small amount of H2Y2- combines with
Mg2+ compared to the amount of H2Y2- that dissociates to give HY3- and H3O+, thus some amount
of sodium ions (Na+) from sodium hydroxide combined with the excess amount of carboxylate
ions remain un-combined from deprotonated EDTA. Dissociation constant K 5 is nearly equal to
the dissociation constant of Magnesium – EDTA complex (KMg2+=2.989 × 10-9). The value of
dissociation constant of Magnesium – EDTA complex (KMg2+) is less than dissociation constant
K3, this show that most of H2Y2- give readily dissociate completely to give HY3- + H+ while the
small dissociation constant of Magnesium – EDTA complex show that there is a dissociation of
MgY2- back to give Mg2+ and Y4-. Where by Y4- accept back the two protons to form H2Y2- that
react with sodium hydroxide during titration to the equivalent point, formation of Na 2Y2-. At the
equivalent point there is a mixture of MgY2- (MgYNa2) and Na2Y2-(Na4Y) since the equivalent
volume of the titration of EDTA mixture with Magnesium chloride is less than the equivalent
volume sodium hydroxide titration of EDTA with sodium hydroxide.
CONCLUSION

Objective of the experiment was to determine the dissociation constant of the Magnesium - EDTA
complex. Determination of the dissociation constant of the Magnesium - EDTA complex was
performed by EDTA potential-titrimetric method using 0.096 M NaOH solution then followed by
titration of the EDTA mixture with Magnesium chloride using 0.096 M NaOH solution and pH
measurement using pH meter. The dissociation constant of the Magnesium - EDTA complex was
2.989 × 10-9.
REFERENCE

Barrow, G.,M., 1979. Physical Chemistry. Fourth edition, McGraw-Hill, New York (Third
edition, 1973, Chapter 2.3-13 to 23-14)
Forland, K., S., 1974. Practicals in Physical and Analytical Chemistry for first year students.
University of Dar es Salaam, Chemistry department, Chapter 08.
Forland, K., S., 1973. Analytical chemistry. University of Dar es Salaam, Department of Chemistry
Kolthoff, I.,M., Elving, P,.J. and Sandell, E.,B., 1959. Treatise on Analytical Chemistry. Part 1,
Vol. 1 Chapter 14, Vol. 2 Chapter 21 section II B, Interscience, New York
Vogel, A.,I., 1978. A Text book of Quantitative inorganic Analysis. Fourth edition Rev. by Bassett,
J., (a.o), Chapter X, 19 – 28, Longmans, London