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16 Water Chemistry
16 Water Chemistry
WATER CHEMISTRY
5.1 INTRODUCTION
Water is surcly God's grecatest gift to mankind. The very existence of life cannot be
imagined without water. One can live without food, shelter or any other thing but life without
watcr is just not possible. Even our body contains around 70% water in it. From an engineer's
point of view. water is no less important. It is roquired in boilers for production of steam, which
acts as a source of energy, as a coolant in many power and chemical plants, in steel, paper,
textile, ice and many other such industrics. Despite its incredible importance, water is receiving
least attention and is getting contaminated in ways beyond description.
Water (H,0) is a polar inorganic compound which is a tasteless, odorless liquid and
colorless compound at room temperature. It is by far the most studied chemical compound and
Is described as the universal solvent. It is the most abundant substance on earth and the only
common substance to exist as a solid, liquid, and gas on earth's surface. It is also the third most
abundant molecule in the universe.
Water molecules form hydrogen bonds with each other and are strongly polar. Its
hydrogen bonding imparts its many unique properties, such as having a solid form less dense
than its liquid form, a relatively high boiling point of 100°C for its molar mass, and a high heat
capacity.
The chemistry of water is based upon its unique physical and chemical properties and
due to its unique properties, water has
acquired special status as a compound. Although there
are no limits to discuss water chemistry, but we will discuss the water
the
chemistry bricfly
under
following important subtitles in this
chapter
() Composition of water
()Structure, bonding and shape of water molecule
(11) Physical properties
(iv) Hardness of water
(233)
234
CONCEPTUAL ENGINEERING C
(v) Polarity and hydrogcn bonding of water and ico NEM13TRY
(vi) Density of water is maximum at 4 degree Celsius
ls s 2p
000
)
Oxygenation in Ground State
Lone pair
ofelectrons
OO
V04.5°
Sp Hybridisation
Thus, there are two unpaired clectrons which can form two bonds with hydrogen atoi
without involving any xCitation Or the oxygen atom. But, in that case, the H,O molecule
WATER CHEMISTRY 235
involving only two orbitals, should have been linear and non polar like BcF,. This is not so
actually. Water molecule is known to have a bent structure and it is highly polar. This is
cxplained on the basis of hybridisation, The central oxygen atom in HaO molec ile has four
orbitals, the two containing lone pairs and thec other two containing bond pairs. These orbiials
undergo sp hybridisation to gnVe four sp" hybrid orbitals of equivalent energy. According
to Sidewick-Powell thcory, these hybridised orbitals give rise to a tetrahedral structure with
two corners occupied by hydregen atoms and tvo corners occupied by lone pairs of electrons.
(Fig. 5.1).
Since, the force of repulsion betwccn the two lone pairs of clectrons amongst themselves
is more than the force of repulsion betivecn a lonc pair and a bond pair which, in turn, is more
than the force of repulsion between two bond pairs of electrons. The two lone pairs will press
the two bonds pairs inward. Conscquently, the bond H-0-H in water will be reduced from
109.5° to 104.5°. The shape of vater molecule as also been explained in furthér chapter.
Most of the unique properties of water are due to presence of H-bonding between its
molecules. Some of the important properties are discussed below:
2. Specificheat ofwater
Water has high specific heat value. This means that water can absorb a lot of heat
before it begins to get hot. That is why water is used in industries and in car radiator as a
coolant. The highest specific heat value of water also help in regulating the rate at which air
changes temperature. The temperature change in between seasons is gradual rather than
sudden, especially near the oceans because of high specific heat value of water.
water has a very high surface tension. In other words, water is sticky and elastic, and
tends to clump together in drops rather than spread out in a thin film. Surface tension is responsible
TOr capillary action, which allows water (and its dissolved substances) to move through the
roots of plants and through the tiny blood vesscls in our bodies
cONCEPTUAL ENGINEERING CHEMISTRY
236
4. Polar Characteristics
Due to its polar character, ionic salt dissolved in it and are ionised in it. Other polar
substances such as alcohols and acids also get dissolved in it. Water is a very good solvent, it is
rarely pure, and some of the properties of impure water can vary from those of the pure
substance. There are also many compounds which are insoluble in water, such as fats, oils and
other non-polar substances
5. Amphoteric Nature
Water is amphoteric, meaning that it is both an acid anda base-it produces H and
OH ions by self-ionization. This means the product of the concentrations ofH and OH is a
constant at a given temperature. the pH value of pure water is 7, which means it contains
equal number of H" ions and OH ions in it and is neutral in nature.
Based on the above mentinoed physical properties of water, the following conclusions
are important:
() The freezing point, boiling point, heat of fusion and heat of vaporization of water are
abnormally higher than those of the hydrides of the other elements of the same group
16 such as H,S, H,Se, H,Te, etc. This is due to the
presence of intermolecular hydrogen
bonding in H,O molecules which is, however, absent among the molecules of HS,
H,Se, H, Te, etc.
() Water has a higher specific hcat, thermal conductivity and surface tension than most
other liquids. These properties allow water to play a vital role in the biosphere. For
example, the high heat of vaporization and the high heat capacity of water are responsible
for moderation of the climate and body temperature of living organisms.
(iv) Heavy water (D,0) has slightly higher values of physical constants because of its
higher molecular mass as compared to that of ordinary water (H,0).
salts of calcium and magnesium. No lather iS formed until all these ions are completcly removed
gets wasted in the process.
and hence a large amount of soap
The main differences between the two types of water are summarized below
Hard water contains dissolved salts 2. Soft water does not contain dissolved
2.
calcium and magnesium salts in it.
of calcium and magnesium in it.
3. In hard water, cleansing quality of soap 3. In soft water, cleansing quality of
is lowered and a lot of it is washed soap s not lowered and so soap is not
during washing and bathing. wasted during washing and bathing.
4. Due to the presence of dissolved hardness- 4. Less fuel and time are required for
producing salts, the boiling point of water cooking in soft water.
is elevated. Consequently, more fuel
and time are required for cooking.
238
cONCEPTUAL ENGINEERING CHEMISTON
CaCO +C0 +H,0 Ca(HC03)2 AISTRY
On boiling,
bicarbonates of calcium and magnesium get decomposed to give insoluhl
carbonates or hydroxides. These carbonates or hydroxides being insoluble ble
are
of precipitates and thus
temporary hardness is removed. removed in fo
orm
caHCO3 CaCO +H,O+ Co,T
MgHCO A Me(OH) +2C0,
Temporary hardness is also called carbonate hardness or
due to the presence of bicarbonates of alkaline hardness. t is
Ca and Mg, carbonates of
small extent and hydroxides of the Fe and other heavy metals
titration with standard acid solution hardness-producing metal ions. It can be determined byto
(say HCl) using methyl orange as an indicator.
(B) Permanent hardness
(non-carbonate or non-alkaline hardness)
It is due to the presence of chlorides and
is calledpermanent hardness, since it cannot be sulphates of calcium
removed by boiling.
and magnesium. It
nylon fabrics.
Calcium and magnesium salts form incrustation inside the
(c) Deposition in kettles: an
kettles, ifhard water is boiled in it. It is duc to the formation of carbonates and hydroxides
boiling water. It wastes fuel. However, this incrustation can be removed by adding
a
in
little vinegar.
and other vegetable do not cook well in hard water.
d) Cooking: Pulses
In paper industry, water is used along with soap for sizing the paper.
(a) Paper Industry:
salts present in it waste a good amount
If hard water is used, calcium and magnesium
of soap by forming insoluble precipitates.
used in textile industry for cleaning, washing and whitening
(b) Textile industry: Water is
hard water is used much soap is wasted.
of yarn. For such purposes, soap is required. If
for dyeing purposes, salts of calcium and magnesium
(c) Dyeing: If hard water is used
not give a homogeneous look.
spoil the desired shade and thus the dyed clothes do
are blocked due to precipitation of salts
(d) Choking and clogging problem: Water pipes
during boilingof hard water. This involves extra cost for maintenance and repair of
water pipes.
3. Problems in boilers
Huge quantity of water is used in boilers for generation of steam. If hard water is used
in the boiler, a number of difficulties arise which are listed as:
-CH-CH-CHhÇH-CH-CH-CH- --.
PROCESS
Column-I: The schematic layout O
of this process is shown in Fig. 5.2. H,CMe,OH H,CNMeOH
Anion exchange resin
The hard water is first passed
through column-I containing cation exchange resins, where all the cations
ions) in water
(Cat or Mg*
present get removed and equivalent amounts of H* ions are released
2 RH+Ca2+
R,Ca+2H
2 RH+Mg" R,Mg+2H*
Column-II: After this, the water is passed though column-II
exchange resins. containing anion
All the anions (HCOg,Clor S0 ions) present in water get removed and cquivalent
amounts of OH ions are released.
ROH+CI R'CI+OH
2ROH+SO R,SO, +20H
WATER CHEMISTRY 241
Impure
water
C 0 , ctc.
(gases)
Alkali for
P
regeneration
Acid for
Degasifier
regeneration Washings HWashings Demineralized
water
Fig.5.2. Demineralization byion exchangers.
H and OH ions, rcleased from cation and anion exchange resins columns, get combined
to give water deionized.
H +OH HO
The water is finally freed from dissolved gases like CO etc. by passing it through a
degasifier. It is a tower heated from sides by steam and it is connected to a vacuum pump. High
temperatureand low pressure reduces the quantity of dissolved gases.
The water coming out is free from all types of ions. Hence, it is called deionized or
demineralized water. It is also free from acidity or alkalinity. It is as pure as distilled water.
Regeneration:
When the cation and anion exchangers stop exchanging H" and OH ions, they are
known as exhausted resins, which can be regenerated as follows:
The exhausted cation exchanger is regenerated by passing a solution of dilute
HCl or
dilute HSO, through column-I.
The regeneration is represented as follows:
0-
&+
-H.
HO+
HO+
Although hydrogen bonding is a relatively weak attraction compared to the covalent
bonds within the water molecule itself, it is responsible for a number of water's
physical
properties. These properties include its relatively high melting and boiling point temperatures:
more energy is required to break the hydrogen bonds between water molecules. In contrast,
hydrogen sulfide (H,S), has much weaker hydrogen bonding due to sulfur's lower
electronegativity. H2S is a gas at room temperature, in spite of hydrogen sulfide having nearly
WATER CHEMISTRY 243
twice the molar mass of water. 1he extra bonding between water molecules also gives liquid
water a largespecifíc heat capacity. 1his high heat capacity makes water a good heat storage
heat shield.
medium (coolant) and
Water molecules stay close to each other (cohesion), due to the collective action of
hvdrogen bonds between water molecules. These hydrogen bonds are constantly breaking,
with new bonds being formed with different water molecules; but at any given time in a sample
of liquid water, a large portion of the molecules are held together by such bonds
Water also has high adhesion properties because of its polar nature. On smooth glass
surface, the water may form a thin Tilm because the molecular forces between glassand iwater
molecules (adhesive forces) are strongerthan the cohesive forces. biological cells and
In
with membrane and protein surfaces that are hydrophilic; that is,
organelles, water is in contact
surfaces that have a strong attraction for water. Irving Langmuir observed a strong repulsive
force between hydrophilic surtaces. To dehydrate hydrophilic surfaces-to remove the strongly
work against thse forces, called
held layers of water of hydration--requires doing substantial
hydration forces. These forces are very large but decrease rapidly over a nanometer or less.
They are important. in biology, particularly when cells are dehydrated by exposure to dry
atmospheres or to extracellular freezing.
H
H-
H
-0
H
-0 - 0
- -0- - -
-O -
H-0, - -
H H
H
(a) (6)
Fig. 5.4. (a) Structure of water in the liquid form
(b) Tetrahedral arrangement of water molecules in ice.
244 cONCEPTUAL ENGINEERING CHEMisTn
RY
In icc. water molecules are tctrahcdrally linked in which two hydrogen ato.
ns form
covalcnt bonds vith oxygen atom whilc the other two hydrogen atoms form hydrogen m
IFig, 5.4 (a)]. This results in the formation of open cage-luke structure as revealed hu bonds
Fig. 5.4(b)]. In ice, covalently bonded hydrogen are at lesser distancc (10A), whereas X-ray
two hydrogen bonds lic at a distance of 1.76A. It results in vacant
(10Å), whercas other
spaces in crystal structuure
and, therefore, gives rise to large volume for a
given mass of water. Therefore, density of iice
which is mass per unit volume is less than that of water
When ice melts, the open cage-like structure (Fig.
5.5) partially breaks, which brings
the water molccules closer by cntering into the vacant
spaces. As a result, volume
and density increases in the liquid state of water. That is decreases
why ice flots on water.
Note that is oxygen atom is linked to four
H-atoms, two by covalent bonds and two by
H-bond. Each water molccule is linked to four water
molecules tetrahedrally by H-bonds.
5.8 DENSITY OF WATER IS MAXIMUM AT 4C
As water is heated form 0°C i.e. 273 K (melting
of hydrogen bonds are broken and the molecules come point ice) onwards, more and more
of
more and more closer in the
As a result, the volume decreases and liquid state.
hence density increases. This
4°C i.c. 277 K, where water attains the process continues up to
maximum density. On heating further, the kinetic
energy of the molecules increases and the molecules move
4C, contraction effect predominates and above 4°C, the apart causing expansion. So up to
and overall expansion dominates over contraction
density decreases. So the value of density is maximum at 4°C.
H H
Vacant Vacant
space space O
H H
Vacant
space
H H
H
Fig.5.5. Open cage-like structure of ice.
The equilibrium constant, K, for the above reaction can be written as:
246
WATER CHEMISTRY
KH0]loH].
1000
Since [H,O] = 8 55.56 M, and remains rather constant under any circumstance,
we usually write,
pKw=-log Kw by definition)
= 14 (at 298 K)
pH=-loglH,0"]
pOH -loglOH]
pH pOH=7 at 298 K; (in neutral solutións)
words, pH+ oPH
=
14
In other
characters
5.9.1 Leveling effect of wåter and acid-base
The strength of strong acids and bases is decided by the self of water. In aqueous
solutions,the strongestacid and base are thehydronium ion, (H0t) and the hydroxide ion
and H,S04 completely ionize
(OH) respectively. Acids such as HCI, HNO3, HCIO3, HCIO4,
water. Furthermore,
in water, making them as strong as H,0* due to the leveling effect of
in their solutions.
strong acids, strong bases, and salts completely ionize aqueous
For example, HCl is a stronger acid than H,0, and the following reaction takes place
when HCl is dissotves in water.
HCI+H0 » C+H,0*
Similarly H,Sso, ionises in water in two steps, because it is a dibasic acid (Basicity = 2)
properties make water an amphiprotic species. In fact, H,O", H,0 and OH are amphiprot
like some other conjugate acid-base pairs of weak acids and bases. protic,
Ifseveral acids and bases are dissolved in water, all cquilibria must beconsidered T"
estimate the pH of these solutions requires the exact treatment of several equilibrium constante
For example, many species dissolve in rain water, and many equilibria must be considered
Detail consideration and examples are given in Acid-Base Reactions.
HC1+H,0 C+H,0 )
H,C-COOH +H,0 H,C-CO0 +H,0* ..i)
Strong acids have a weak conjugate bases and vice versa.
For example, CF ion is weak conjugate base of the
strong acid HCl and H,C-CO00
ion is a strong conjugate base of the weak acetic acid
(CHCOOH).
HCI, being a strong acid ionizes completely and reaction (i) take place in the forward
direction. C ion being a week base cannot bring out the backward reaction.
Acetic acid (CH,COOH) being a weak acid does not ionise fully in the forward direction.
The acetate ion (H3C-COo) being
place in the backward direction.
astrong conjugate base favours the reaction (i) to take
Carbon dioxide in the air dissolve in rain water, lakes and
rivers, A solution of CO2
involves the following reaction:
2H,0(g) 2H(g)+0,(8)
WATER CHEMISTRY
247
Water also decomposes into its clemonts; when olectricity is passed through it in
prescnce
small amount of an acid or an alkali,
of a
2H,O(0)Electriccuront
2H2(8)+ 02(8)
(At cathodo) (Al anoda)
2.Acid-base character
Water undergoes ionization to a small extent to give H30* (aq) and OH (aq) ions. As
has very low clectrical conductivity.
a result, pure water
H,00)+H,o)H,0'(aq)+OH"(aq)
Thus, water acts both as an acid and as a base and hence is sald to he amphoteric
in character.
For example, it can act as an acid towards NH2 and as a base towards H,S
3. Redox reactions
Water also undergoes oxidation-reduction reactions.
(i) As an oxidising agent: Water reacts with number of active metals like Na, Ca, ctc.
liberating hydrogen gas.
C(s)+Ho(g).
(Reductant) Ni Co(g)+H2(8)
(Oxidant)
Syngas
In all these reactions, water acts as an oxidising agent and hence itself gets reduced
to hydrogen gas.
248
cONCEPTUAL ENGINEERING CHEMISTO
(ii) As a reducing agent: Water reacts with highly clectronogative clements like fuoe
liberating dioxygen and trioxygen rine
249
AIN (5)43 HO0) AOH), (aq) NH,(g) +
Aluminium nitride
Ammonia
CaP2s) +611,0) -> 3
Ca(OH), (aq) +2 PH,(g)
Calcium phosphide
Phosphine
Na,CO, (s) +
2H,00) 2 NaOH (aq) +
H,Co, (aq)
Since the hydrolysis of Na,CO, produces a
acid
strong base (NaOH) and a weak acid, i.e.,
carbonic (H2C03), thercfore, an aqueous solution of Na,CO, is alkaltne in nature.
In contrast, the hydrolysis of CuSO produces a weak base i.e.,
Cu(OH),
acid (H,SO4) thercforc, an aqueous solutton of CuSO, is acidic in nature.
and a strong
molecules (hydration). The rolatively small size of water moleculcs allows by iwater
by
H, H
--
WATER CHEMISTRY
H,o(+H,S(aq)>H,o*
Base Acid2 Acid
(aq) +HSBase2(aq)
Problem 5. Consider the.reaction of water with F2 and
and reduction, which
suggest, in terms of ozidation
species are oxidised/reduced ?
Solution. 2F,(8)+2H,O() +
0,(g)+4H* (aq) +4F" (aq)
(Oxidant) (Reductant)
or
3F(g) +3H, O0)0,(g)+6H* (aq)+6F (aq)
(Oxidant) (Reductant)
In these reactions, water acts reducing agent and therefore, itself gets oxidised to
as a
either O, or Og while F2 acts as an oxidising agent and hence, itself reduced
to F ion.
Problem 6. What the temporary and permanent hardness of water ?
causes
H,O0+HS(aq)
Base
H,0* (aq) +HS (aq)
Acid Acid Base2
H,O(+ NH, (aq) NH; (aq+OH (aq)
Acid Base2 Acid2 Base
Problem 10. What properties of water make it
useful as a solvent ? What type of
compounds can it (i) dissolve (ii) hydrolyse ?
Solution. (i) Water has a high dielectric constant
Because of these properties, water dissolves (79.39) and high dipole moment (1.84 D).
most of the
many covalent inorganic (ionic) compounds and
compounds. That is why water, is called a universal solvent.
Whereas ionic compounds dissolve in water due to
ions, covalent compounds such as alcohols, amines, urea, ion-dipole interaction or salvation of
due to H-bonding. glucose, sugar, etc. dissolve in water
(ii) Water can hydrolyse many oxides (metallic or
non-metallic),
phosphides and other salts. In these reactions, H" and OH- ions ofhydrides, carbides, nitrides,
water interact with anions
and cations respectively leading to the formation of an
acid or a ba[e or both as shown below:
Ca0 (s)+H,0 ()
Ca(OH)2 (aq)
SO (g)+Ha0 ()>H,S0, (ag)
CaH, (s)+2H,00) Ca(OH), (aq) +2 H (g)
CaC2 ()+2H,0 ( Ca(OH)> (aq)+ HC=CH(g)
Acetylene
Problem 12. What is the difference between the terms
'hydrolysis' and 'hydration' ?
Solution. Interaction of H* and OH- ions of
H,0 with the anion and the cation of a salt
respectively to give the original acid and the original base is called hydrolysis. For example,
Na,CO +2H,0 2 2 NaOH + N,CO3
Salt Base Acid
253
WATER CHEMISTRY
On the other hand, hydration mcans addition of H,O to ions or molecules to form
ions hydrated
or salts. For cxamplc,
hydrated
Na'Cl (s) +H,0 () Na (aq)+ C (aq)
Salt
CuSO (s) + 5 H,0 () CuSO.5 H,0 (s)
(Colourless) (Blue)
13. Knowing the properties of H,0 and D,0, do you think that D,0 can be
Problem 13.
drinking purposes ?
used for
an Hcavy water is injurious to human beings, plants and animals since it slows down the
rates of reactions occurring in them. Thus, heavy water does not support life so well as does
ordinary water.
Problem 17. Why is sodium chloride less soluble in heavy water than in ordinary water?
Solution. Due to lower dielectric constant of D,0 over H,0, NaCl is less soluble in D,0 than
in H,0.
Problem 18. Explain why electrolysis of ordinary water occurs faster than heavy water?
Solution. Due to lower bond dissociation energy of protium bonds in H-0-H than deuterium
bonds in D-0-D, electrolysis of H,0 occurs much faster than that of D,O.
Problem 19. The boiling point of H,O is higher than that of H,S. Explain.
Solution. Due to extensive intermolecular H-bonding in H,0, the b.p. of H,0 is much higher
than that of H,S.
Problem 20. What do you mean by hard and soft water.
Solution. The water which does not produce lather with soap solution, but forms a white
precipitate is called hard water. it contains dissolved calcium and magnesium salts which torm
scum with soap solution.
Soft water gives lather with soap solution not contain dissolved salts
readily. It does
and so it forms lather rather than scum or precipitate with soap solution.