CALCIUM AND MAGNESIUM CONTENT BY TITRATION

THEORY
When we refer to a hard water solution, we mean a solution containing appreciable
amounts of calcium (Ca
+2
) and magnesium (Mg
+2
) ions. This hard water may include
other components such as solids, oil, dissolved gas, or other negative and positive ions,
but it is mainly calcium and magnesium ions dissolved in the water that make it hard,
thus tending to deposit scales of calcium carbonate (CaCO
3
and magnesium carbonate
(!gCO
3
.
With the presence of Ca
+2
, Mg
+2
, bicarbonate ("CO
3
#
and a p"$%, massive scale
formation occurs.
C"&!'C() *&(CT'O+,-
+atural waters, oil formation waters and heat transfer fluids usually contain the hardness
causing ions of Ca
+2
, Mg
+2
, and HCO
3
-
. When these waters are heated and the p" is near
or greater than %, scaling results. Water sometimes contains Fe
+2
and Ba
+2
ions that will
also form carbonate scales.
C"(*(CT&*',T'C, O. "(*/ W(T&* ,C()&,-
0. !ost scales deposit in pipes in an annular growth ring pattern.
1. 'f not controlled, scales will eventually plug the pipe.
3. These scales do not conduct heat well and act as an insulator, causing e2treme hot
spots in boiler tubes.
3. These scales are brittle in nature and often flake off, causing wear on pump
impellers and plug filter screens.
4. These scales are not uniform in nature and corrosion may develop under a loose
flake of scale.
5. ,caling can be so severe that a four#inch boiler tube will plug solid, in less than a
week, if untreated water is used.
"(*/ W(T&* T*&(T!&+T,-
"ard water can be softened by many techni6ues we will be studying. Water treatment
can lower the concentration of hard ions to an acceptable level. 'on e2change can
substitute softer sodium ions for the hard ions, making the water soft but also corrosive.
Once an acceptable level of hardness has been achieved, scale formation can be
controlled by various additives
"(*/ W(T&* ,C()& *&!O7()-
Once scales are formed they can be removed slowly by changing the water chemistry and
actually dissolving the formed scale. ,cales can be mechanically removed by reaming, a
type of mechanical machining inside the pipes. ,cales can also be removed by acidi8ing
with strong mineral acids, such as "Cl, containing inhibitors that will prevent the pipes
from being dissolved.
'f the scale contains .e,, ferrous sulphide, which is a black colored band of precipitate,
then e2treme care has to be followed since deadly "
1
,, hydrogen sulphide, gas is
liberated on acidi8ing.
!&T"O/ O7&*7'&W-
To determine the hardness of a water sample, technologists use the EDTA
(ethylenediaminetetraacetic acid) titration. &/T( disodium salt is a soluble salt that
reacts readily with all 91 ions, namely Ca
+2
, Mg
+2
, Fe
+2
and Ba
+2
. The &/T( anion
reacts 6uickly with any 91 metal to form a soluble metal &/T( comple2. &/T( is
called a chelating or sequestering agent since it will react with and tie up heavy metal
ions and render them harmless to humans and water systems.
(ll metal#&/T( salts are colourless and re6uire an indicator to tell us when the reaction
is over. 7arious hardness indicators have been developed. They all tell the operator
when the titration is complete. "ardness indicators are large comple2 organic dyes that
react with &/T( to form coloured comple2es. &/T( reacts preferentially with highly
mobile metal ions, but once they are all tied up, the &/T( will react with the slow
moving, massive dye molecules to give an endpoint. (s a conse6uence, endpoints are
challenging.
We will use &riochrome :lack T for the total hardness endpoint, which includes the sum
of calcium and magnesium ions. !ure2ide indicator gives us the calcium endpoint.
TOT() "(*/+&,, *&(CT'O+-
C()C';! *&(CT'O+-
T"& 7O);!& /'..&*&+C& O. &/T( T'T*(T&/ :&TW&&+ T"& TOT()
"(*/+&,, (+()<,', (+/ T"& C()C';! (+()<,', ', T"& !(=+&,';!
*&,;)T.
Total hardness # calcium hardness > magnesium hardness
!(T"&!(T'C() *&)(T'O+,"'?,-
Molarity of EDTA soltion is !"!# M
$% of !"!# M EDTA & # $g of CaCO
3
EDTA $olarity ' EDTA (ol$e (%) & Ca
+2
$olarity ' Ca
+2
(ol$e (%)
or, sing (ol$es
PROCEDURE
C()C';! "(*/+&,, /&T&*!'+(T'O+
0. .ill a 4@ m) burette with @.@0 ! &/T( solution, making sure the tip is full and
free of air bubbles. ,et ,tart volume.
1. (dd 4@.@@ m) of an unknown hard water solution into a 0@@ m) beaker.
3. Obtain !agnetic ,tirrer from &6uipment menu. ?lace beaker on stirrer. 'ncrease
,tir from the conte2t menu.
3. (dd 3 m) of 0.@ ! ,odium "ydro2ide.
4. (dd 0@@ mg of !ure2ide indicator.
5. Titrate with the @.@0 ! &/T( until the colour changes from salmon pink to
orchid purple. *ecord all pertinent data on data sheet. *ead burette to 9A# @.0@
m).
%. *epeat the titration until the final volumes agree to 9A# @.1@ m).
TOT() "(*/+&,, /&T&*!'+(T'O+
0. .ill a 4@ m) burette with O.0 ! &/T( solution, making sure the tip is full and free
of air bubbles. ,et ,tart volume.
1. (dd 4@.@@ m) of an unknown hard water solution into a 0@@ m) beaker.
3. Obtain !agnetic ,tirrer from &6uipment menu. ?lace beaker on stirrer. 'ncrease ,tir
from the conte2t menu.
3. (dd 0@ m) of (mmonia to the beaker.
4. (dd 0@@ mg of &riochrome :lack T indicator.
3. Titrate with the @.@0 ! &/T( until the colour changes from wine red to pure blue.
*ecord all pertinent data on data sheet. *ead burette to 9A# @.0@ m).
5. *epeat the titration until the final volumes agree to 9A# @.1@ m).
'ncidentally, &/T( is a common food additive that is used in salad dressing and other
spicy condiments. 't is totally safe for sink disposal.

BE CAREFUL WITH CALCIUM AND TOTAL HARDNESS BUFFERS
Spills on your skin or !" #loor $r" %orrosi&" $n' s!oul' (" )$s!"' o## )i! so$p
$n' )$"r i**"'i$"ly+ B" sur" o )"$r your s$#"y ,l$ss"s $ $ll i*"s $s
p"r*$n"n (lin'n"ss %$n "$sily r"sul #ro* sron, ($s"s spl$s!"' ino your "y"s+
DO NOT )"$r %on$% l"ns"s+ Ask your insru%or #or #ur!"r in#or*$ion+
REPORT

-+ PLEASE SHOW DETAILED CALCULATIONS FOR THE FOLLOWING.
!olarity of calcium in unknown-
ppm calcium in unknown-
ppm calcium carbonate in unknown-
7olume of &/T( for magnesium portion-
ppm magnesium in unknown
Questions
0. ( corrosion technologist pipetted a 0@@.@@ m) hard water sample and titrated it
with 3%.53 m) of @.@0 ! &/T( solution for a total hardness endpoint, and 1B.31
m) of @.@0 ! &/T( solution for a calcium endpoint. Calculate the concentration
of magnesium and calcium in ppm. *ecord your answers as ppm Mg
2+
, and Ca
2+

espectively. .or each answer indicate the ppm as CaCO
3
also.
1. Write and balance the reaction between the magnesium ion, the bicarbonate ion
and heat.
3. Write and balance the scale removal reaction involving the scale generated in
6uestion C1 with HCl.
3. 'n a sour water system (H
2
)) there is an opportunity for ferrous sulphide to form
along with the calcium and magnesium carbonate scales. 'f acidi8ing is used to
clean away scales, what danger e2istsD 'ndicate this by using a balanced reaction.
4. 'n the field, where the scale in 6uestion C3 is removed by acidi8ing, what
precautions should be takenD

+(!&- EEEEEEEEEEEEEEEEEEEEEEEEEEEE
,&CT'O+- EEEEEEEEEEEEEEEEEEEEEEEEE /(T&-
EEEEEEEEEEEEEEEEEEEEEEEEEEEEEE
CALCIUM CONTENT OF A HARD WATER
;+F+OW+ '+.O*!(T'O+ .*O! )(:&)-
EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE
CO+C&+T*(T'O+ O. ,T(+/(*/'G&/ &/T(
,O);T'O+-EEEEEEEEEEEEEEEEEEEE
Tri$l /- Tri$l /0 Tri$l /1
,ample volume
.inal burette reading
'nitial burette reading
7olume titrated
(7&*(=& O. 1 :&,T T'T*(T'O+H,- EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE
CALCIUM AND MAGNESIUM CONTENT OF A HARD WATER
Tri$l /- Tri$l /0 Tri$l /1
,ample volume
.inal burette reading
'nitial burette reading
7olume titrated
(7&*(=& O. 1 :&,T T'T*(T'O+H,- EEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEEE