Chpt.

19: Environmental
Chemistry - Water
Water is essential for life:

- 80% earths surface covered with water

- makes up 2/3 of body weight
- can live without food for several weeks but
can only survive without water for few days

We take water for granted!!!! When we turn on the tap

we expect to have a plentiful supply of clean safe drinking
water that we use for cleaning, washing etc. We forget
that as a country with piped water system we are in the
minority!!!!!
In this chapter we will study and gain an appreciation for
the importance of water in our lives. We will investigate:

- water as an important solvent

- how substances dissolved in water affect its
properties
- how water is treated in water treatment plants
- water pollution
- analyse the composition of water
- how sewage is treated
 Hardness In Water

Definition:
Hard water is water that will not easily form a lather
with soap. Hardness in water is caused by the presence
of Ca2+ and Mg2+ ions.

• A grey precipitate (scum) is formed instead

• Hardness caused by dissolved calcium and magnesium
salts:
- calcium sulphate - CaSO4, magnesium
sulphate - MgSO4

- calcium chloride - CaCl2, magnesium

chloride - MgCl2

- calcium hydrogencarbonate - Ca(HCO3)2,

magnesium - Mg(HCO3)2
• One of the most common substances in soap is sodium
stearate, C17H35COONa. When soap is added to Hard
Water the stearate ion (active part of soap) reacts with
the calcium or magnesium ions in the water to form the
grey insoluble compound calcium stearate (scum)
 Calcium ion + Stearate ion → Calcium Stearate (scum)

Ca2+ + 2C17H35COO- → (C17H35COO)2Ca↓

• Lather is only formed once all the Ca2+ /Mg2+ ions

have been precipitated in the scum – great deal of
soap wasted in reaching this stage
• Modern detergents (washing powders, washing up
liquids, shampoos etc.) not affected by hard water as
they DO NOT contain soap – made from crude oil
Types of Hardness:

• Permanent and Temporary

• Expressed as ppm
Temporary Hardness:

Temporary hardness is hardness in water that can be

removed by boiling.

Caused by:
- calcium hydrogencarbonate – Ca(HCO3)2
- magnesium hydrogencarbonate –
Mg(HCO3)2
Limestone (calcium carbonate) is insoluble in water thus
calcium ions are not immediately available to cause
hardness
However, limestone does react with carbonic acid:

Rainwater + CO2 → Carbonic Acid

H2O + CO2 → H2CO3

This acidic solution of carbonic acid reacts with the

limestone in the soil to form calcium hydrogencrbonate:
Limestone + Carbonic Acid → Calcium
Hydrogencarbonate
CaCO3 + H2CO3 Ca(HCO3)2
INSOLUBLE SOLUBLE
The Ca2+ ions cause hardness while the HCO3- ions have
no effect. However, if water containing these two ions
is heated the water is softened as a chemical reaction
occurs which removes the Ca2+ ions from the water:
HEAT
Calcium → Calcium Carbonate + CO2 + H2O
Hydrogncarbonate

Ca(HCO3)2 → CaCO3↓ + CO2 + H2O

Soluble Insoluble
An undesirable side effect of this is that the insoluble
calcium carbonate precipitate can form a fur/scale that
builds up on kettles, boilers, hot water pipes etc. The
build up of this limescale can cause problems such as
wasting heat, or even explosions due to pipes being
completely clogged!!!
*Note: Mg2+ ions often come from dolomite rock, which
contains a mixture of MgCO3 and CaCO3 (MgCO3.CaCO3)

*Demonstration: Test on scale deposits in a kettle

Permanent Hardness:

Permanent hardness is hardness in water that can only be

removed by methods other than boiling i.e. ion exchange,
distillation

Caused by:

- sulphates of calcium (gypsum rock) and

magnesium

- chlorides of calcium and magnesium

Methods of removing hardness (permanent & temporary)
from water:

a) Distillation

b) Washing Soda

c) Ion Exchange Resin/Deionisation

a) Distillation:

- involves boiling the water and then cooling

the vapour

- ALL dissolved and suspended solids and

dissolved liquids are removed from the water

- very pure water

- not used on a large scale to soften water due

to the expense involved in boiling the water
Distillation
b) Washing Soda (Hydrated Sodium Carbonate –
Na2CO3.10H2O)
Before the development of modern detergents clothes
were washed with soap and crystals of this compound
were added to the water to soften the water!!!
- carbonate ions in the washing soda react with
Ca2+ ions in the water and removes them as
insoluble calcium carbonate:
Ca2+ + CO32- → CaCO3↓
- Na+ ions (sodium carbonate) remain dissolved in
water
- bath salts – crystals of washing soda coloured
with perfume added
c) Ion Exchange Resin/ Deionisation (Swap Shop):
Easiest way to remove hardness from water

Modern ion exchange resins are man-made materials

which exchange or ‘swap’ ions that cause hardness (Ca2+,
Mg2+) with ions that do not cause hardness (Na+).

Ion exchange units used to soften water contain cation

(positive ion) exchange resin
- Ion exchange involves the water being passed
through a cation exchange resin.

- The resins used are complex sodium compounds

and may be represented as RNa.

- The Ca2+ and Mg2+ ions in the hard water swap

places with the Na+ ions in the resin:
Learn:
2RNa(s) + Ca2+(aq) → R2Ca(s) + 2Na+(aq)

- Eventually the resin loses all of its Na+ ions and it

needs to be regenerated by passing a concentrated
solution of sodium chloride through it
Ion Exchange Resin
c) Deionisation

In some cases it is necessary to remove ALL the ions

from the water i.e. deionised water. In this case:
- the resin used is a mixture of a cation (+ive)
exchanger, replaces metal ions in water with
hydrogen ions, H+, and an anion (-ive) exchanger,
which replaces anions in water with hydroxide ions,
OH- - MIXED BED RESIN
Removal of Na+ and Cl- ions in water using a
deioniser:
*Learn:
- Cation exchange resin, RH, replaces Na+ ions
with H+ ions:
RH + Na+ → RNa + H+

- Anion exchange resin, ROH, replaces Cl- with

OH- ions:

ROH + Cl- → RCl + OH-

- H+ and OH- ions then combine to form water:

H+ + OH- → H2O
Deionisation
 Deionised Vs. Distilled
(Higher Level)

Deionised Distilled
• Easily and cheaply • Expensive to produce
produced
• Purest form of water
• Can contain dissolved as all dissolved and
gases as well as non- suspended solids as
ionic material well as dissolved
(organic) dissolved in gases have been
the water removed
 Advantages & Disadvantages of Hard Water
Advantages Disadvantages
Provides calcium Blocks pipes leaves
for teeth and bones scale on kettles and
boilers
Nicer taste Wastes Soap
Good for brewing Produces scum
and tanning

Student Questions:
- Bk pg’s 288-289 Questions 19.1-19.2
- Workbook pg. 48 Question W19.1
Mandatory Experiment: To determine the total
hardness in a water sample (Higher Level)
Must understand
- theory behind this experiment
- theory of experiment
- associated calculation
- how to determine the concentration of
temporary and permanent hardness

Student Questions:
- Bk pg. 289 Questions 19.3 and 19.4, 19.5 (Tricky)
- Workbook pg’s 48-49 Questions W19.2-W19.5
 Water Treatment
Water supplied to houses around the country must
fulfil certain criteria. It must be attractive looking,
odourless, safe to drink and fluoridated. In order to
ensure that the quality of domestic water supplies is of
a certain standard it is necessary to carry out certain
procedures on the water before going to houses. Water
treatment plants have been set up around the country
to ensure this standard is reached.
Stages of Water Treatment:

1. Screening
2. Flocculation
3. Settlement (Sedimentation)
4. Filtration
5. Chlorination
6. Fluoridation
7. pH adjustment
1. Screening:
Water is first passed through a wire mesh to
remove any floating debris – twigs, plastic bags
etc.
2. Flocculation:
Flocculation is the coming together of small `
suspended solids in water to form larger
particles (flocs)
This is done by adding certain chemicals to the
water – flocculating agent Al2(SO4)3
A flocculant is a chemical added to water to
coagulate suspended particles
The addition of Al2(SO4)3 causes the suspended
solids to stick together to form larger particles,
which are allowed to settle out in the
settlement stage.
Flocculation
3. Settlement (Sedimentation):
The flocculated water is pumped into the bottom
of large settlement tanks and rises up slowly
(allows maximum settlement to take place at
bottom of tank) to the surface where clear water
is collected in channels

The suspended particles settle to the bottom

Approximately 90% of particles are removed in

settlement stage
Settlement
4. Filtration:
The water, from top of settlement tanks, is
allowed to fall through beds of graded sand and
gravel

These filter beds remove any remaining

suspended solids

The sand acts just like a sieve or filter paper in

removing the suspended solids

The water coming out of filter beds is now clear

but not yet fit for human consumption
Filtration
5. Chlorination:
Chlorine is added to water in order to sterilise it
i.e. kill any harmful micro-organisms
Chlorine may be added as elemental chlorine or
more commonly in the form of sodium
hypochlorite (NaOCl) (active disinfecting agent
chloric(I) acid)
Chlorine requirements in drinking water 0.2-0.5ppm
Chlorine requirements in swimming pool water 1-
5ppm
Amount of chlorine added must be carefully
controlled need enough to give continued
protection until use but also not too much as gives
water unpleasant taste and smell.
Chlorination
6. Fluoridation:
Involves adding small quantities (1ppm) of
fluorine compounds to water

Fluoridation of water is carried out because it has

been shown that the presence of fluoride ions in
water can help prevent tooth decay –
strengthens enamel of teeth

Sources of fluoride ions:

- sodium fluoride, NaF
- hexafluorosilicic acid, H2SiF6
Fluoridation
7. pH Adjustment:
It may be necessary to adjust the pH of water
before it leaves treatment plant

Optimum pH of water for distribution – pH 7-9

If water supply slightly acidic (due to original

source or chemicals added) can lead to corrosion of
pipes so calcium hydroxide (lime) added to raise
pH above 7

If water supply slightly basic (due to added

softeners-sodium carbonate) sulphuric acid added
to lower pH.
pH Adjustment
Mandatory Experiment: To determine

(a) the total suspended solids (p.p.m) of a sample of

water by filtration
(b) the total dissolved solids (p.p.m) of a sample of
water by evaporation
(c) the pH of a sample of water

Must understand:
- theory of experiment
- associated calculations
Student Questions:

Book – pg’s 289-230 Questions 19.6

Workbook – pg. 49 Question W19.6
Water Pollution
Dissolved Oxygen:

Dissolved oxygen in rivers, lakes and the sea is vital

for the survival of fish and other forms of life.
Although oxygen (non-polar) is only slightly soluble in
water aquatic life cannot exist without it.
The solubility of oxygen in water is dependent on the
temperature of the water – the solubility of gases in
water decreases with increase in temperature - when
water is heated bubbles of air are seen to come out of
solution.
Another factor affecting the amount of dissolved oxygen
in water is the discharge of organic waste (domestic
sewage, animal slurry, silage effluent etc.) into
waterways.
When organic waste is discharged into the water, the
bacteria and other organisms which are naturally present
in the water are provided with nutrients.
These nutrients cause the organisms to multiply into
large numbers. As the organisms break down the waste
(aerobic respiration) into compounds like CO2 and
water, they use up the oxygen dissolved in the water:

Organic Matter + Oxygen CO2 + H2O

If a considerable amount of organic waste is present, it is
possible that the dissolved oxygen level in the water will
be reduced so much that fish life in the water will start to
decline e.g. trout and salmon require 5 p.p.m of dissolved
oxygen in order to survive.

If the dissolved oxygen level drops to low levels such as

zero concentration, anaerobic bacteria will take over and
start producing H2S gas leaving the river with a foul
smell!!!!

Such POLLUTION results in the death of vast amounts of

fish and other aquatic life!!!!!
Biochemical Oxygen Demand (B.O.D.) (Higher Level):
The Biochemical Oxygen Demand (B.O.D.) test was
developed to determine the level of pollution in our
waterways:

Biochemical Oxygen Demand is defined as:

- the amount of dissolved oxygen

- consumed by biological action
- when a sample of water is kept at 20oC
- in the dark
- for five days

*Note: B.O.D. is measured in mg/L of oxygen

This process involves collecting two water samples from
the same area. The dissolved oxygen in bottle A is
measured immediately using a titration called The
Winkler Method (or using a dissolved oxygen meter).
Bottle B is incubated in the dark at 20oC for five days:

- kept in the dark to prevent the production of

oxygen by photosynthesis that might be carried out
by any plant life present.

- amount of oxygen dissolved in water depends on

temperature, experiment is carried out at a fixed
temperature to allow the valid comparison of the
BOD values of different water samples.
- the Winkler method of measuring dissolved
oxygen is carried out on the sample of water in
bottle B at the end of the 5 day period. The
difference between the dissolved oxygen level for
bottle A and the dissolved oxygen level for bottle B
is the B.O.D. This B.O.D. value represents the
amount of oxygen required by bacteria and other
micro-organisms to break down organic material
over the five day test period.
- if the sample is very polluted, (effluents with
BOD greater than 9mg/L) it must be diluted by a
fixed amount with well-oxygenated water. This
ensures that the dissolved oxygen present does
NOT run out before the end of the 5 day test
period and that a measureable amount of oxygen
(at least 2 p.p.m) will be left after the five day
period. When the B.O.D. calculation is carried out,
the result is multiplied by the dilution factor to
get the true B.O.D. value.

- The higher the B.O.D. value the more polluted the

water. A high B.O.D. value means that there is a
large amount of organic waste in the water and as
this organic waste is acted on by bacteria, the level
of oxygen decreases.
 B.O.D (mg/L) Source of sample
1-2 Clean Water
20-40 Treated Sewage
100 Polluted Water (fish
die)
30,000 Pig slurry
54,000 Silage Effluent

Most fish kills in Ireland are caused by slurry and silage

effluent into rivers and lakes
Example 1:
To find the B.O.D. of a sample of polluted river water, 25cm3 of
the water was diluted to one litre with well-oxygenated pure
water. Two bottles, A and B, were filled with the diluted water
and their dissolved oxygen concentrations were determined.
The analysis was carried out immediately for bottle A and five
days later for bottle B. The results obtained were 12.8 p.p.m and
8.2 p.p.m respectively.

i) Why dilute polluted river water? What was advantage in

using well oxygenated water for this purpose?
ii) Under what conditions should bottle B have been kept for
the five days before it was analysed? In the case of one of
these conditions explain why it is necessary.
iii) What was the B.O.D. of the polluted river water?
Example 1 Solution:
Example 2:

Why is it necessary to analyse the sample of water in

bottle A immediately???

Example 2 Solution:

• So that oxygen content does not increase due to

photosynthesis
• So that the oxygen content does not decrease due to
respiration
• So that the oxygen content does not
increase/decrease due to activity of organisms
Example 3:
A sample of polluted water was analysed, in order to
determine the amount of dissolved oxygen in the water, using
the Winkler method. The main reactions may be represented
as follows:
4Mn(OH)2 + O2 → 2Mn2O3 + 4H2O
Mn2O3 + 2I- + 6H+ → 2Mn2+ + I2 + 3H2O
A 50cm3 sample of the water was diluted to one litre with pure
well-oxygenated water. 300cm3 of this diluted solution were
analysed by the Winkler method and 14.7cm3 of 0.02M sodium
thiosulphate were required. A second 300cm3 sample was
stored in the dark at 20OC for five days and then analysed for
dissolved oxygen. The liberated iodine required 4.8cm3 of
0.02M sodium thiosulphate. Calculate the amount of dissolved
oxygen in each sample of water. Express your answers in p.p.m.
Hence find the B.O.D. of the water.
Example 3 Solution:
Student Question:
Please complete W19.8 pg 50 in workbook

Try the following:

Book – pg 290 No’s 19.7 – 19.9
Workbook – pg. 49 W19.7
Mandatory Experiment: To measure the amount of
dissolved oxygen in a sample of water by means of a
redox titration (Winkler Method)

Must understand:

- reaction equations
- theory of experiment
- associated calculations (calculating amount of
dissolved oxygen in water in p.p.m.
Eutrophication:
Another process which results in the reduction of the
amount of dissolved oxygen in water is
EUTROPHICATION.
Defnition:

Eutrophication is the enrichment of water with nutrients,

which leads to excessive growth of algae
This is caused when water is overloaded with plant
nutrients, in particular nitrate ions (NO3-) and phosphate
ions (PO43-). This is caused by untreated or partially
treated sewage or by run off from farmland of slurry or
fertilisers.
As the nitrate and phosphate levels rise, many plants
and floating algae undergo population explosions.
The algae are short lived.
As the algae decay, micro-organisms use up much of the
dissolved oxygen in the water, leading to the death of
many forms of animal life.
‘Algal Bloom’ covers much of the
surface of the water with a green
scum
 Higher Level
Eutrophication may occur artificially or naturally

Natural Eutrophication:
- occurs mainly in lakes
- when sediments build up in a lake leads to a
gradual increase in nitrogen and phosphorous
levels.
Artificial Eutrophication:
- caused by a sudden increase in nutrients
- source of these nutrients – artificial fertilisers
being washed into rivers and lakes or by domestic
sewage/waste from farming entering waterways
 There is some concern about the levels of
nitrate ions in water. It is thought that high
levels of nitrates may cause stomach
cancer and also death in babies.
Heavy Metal Pollution (Higher Level):
Water pollution is also caused by the release of toxic
metal ions into the water e.g. lead ions (Pb2+) , mercury
ions (Hg2+) and cadmium ions (Cd2+)
• These elements considered cumulative poisons
i.e. frequent exposure causes a build up in the
body, with consequent serious health damage.
• Quantities of these elements can be found in
rivers and lakes as a result of the discharge of
industrial effluents or the dumping of batteries
that contain these metals.
• Consequently they can enter drinking water!!!!!
• Associated problems:
- lead in drinking water - old houses
containing lead plumbing

- mercury poisoning – metallic mercury is

dangerous when inhaled but less
dangerous when swallowed as most of it
passes out of body within a few days.
However, it is a build up of mercury salts
which can pose serious health risks! –
Minamata Bay 1950’s – birth defects and
death
• Before the effluent is run into a waterway, the
metal ions are removed by means of
precipitation – lead ions are reacted with dilute
HCl:

Pb 2+ + 2Cl- → PbCl2↓
 EU and Water Quality
Water quality is controlled by EU legislation. Heavy
metal limits have to be set because of the toxic effects
of metals like mercury, cadmium and lead. Limits on
phosphates and nitrates help to reduce the occurrence
of eutrophication in waterways. Limits are also set for
chemical species dissolved in drinking water.
Cadmium – 5 mg/L

Mercury – 1 mg/L

Lead – 10 mg/L

Nitrates – 50 mg/L
 Sewage
Treatment
For many years, domestic sewage running untreated into
rivers, lakes and the sea has been one of the most serious
causes of pollution in Ireland. In general a small quantity
of a pollutant would not pose a problem as it would be
degraded quickly, posing no threat to the environment.
However, large quantities of sewage cannot be broken
down in a reasonable period of time and so constitutes
serious pollution.

Sewage may consist of organic waste, inorganic waste

and various gases. If this were simply dumped into a
local river or lake there would be such a high demand on
the dissolved oxygen that the water would become very
polluted!!!
The essential purpose of a sewage treatment plant is
to reduce the B.O.D. of the sewage before it is
discharged into the local river or lake.

There are three recognised stages in sewage

treatment:

- Primary Treatment

- Secondary Treatment

- Tertiary Treatment
Primary Treatment (Mechanical Process):
• Involves screening and settling
• Screening: sewage passes through steel bars that
remove large floating solids and physically break
up sewage. Sewage is then slowly passed through
grit channels in which pebbles, grit etc. settle and
are removed periodically.
• Sewage flows into bottom of primary settling
tanks where it remains for a few hours.
• Settlement (Sedimentation): suspended solids
settle to the bottom of the tank and form a
sludge. Scraper at bottom of tank removes sludge
periodically.
 • Liquid on top (supernatant liquid) flows away to
secondary treatment.
• Removes approx 1/3 B.O.D. in sewage
Definition:
Primary treatment involves screening and settlement,
and is a physical process.
Secondary Treatment (Biological Oxidation of Sewage):
• involves biological process which reduces the
levels of suspended and dissolved organic
materials – ACTIVATED SLUDGE PROCESS
• consists of an aeration tank followed by a settling
tank.
• Aeration Tank: The sewage is fed continuously into
an aerated tank that is kept oxygenated by
mechanical agitators. Micro-organisms present in
the tank oxidise most of the organic matter
(activated sludge)
*Note: function of aeration tank is to breakdown
organic matter without letting the concentration of
dissolved oxygen in the liquid drop too low.
• After the biological stage the sewage flows into a
settling tank where it undergoes further
settlement.
• Settling: some of the sludge (rich in nutrients) is
removed and used as fertiliser or further
converted to methane. Some of the sludge is
recycled back into the aeration tank to come in
contact with fresh sewage.
• Thus the micro-organisms are continually
decomposing the organic waste in the sewage
into compounds like carbon dioxide, nitrates etc.
 • After secondary treatment about 95% of the
B.O.D. of the original sewage is removed.
• Effluent may now be discharged into waterways,
however, still contains compounds of
phosphorous and nitrogen – moves to tertiary
treatment.
Definition:
Secondary treatment is a biological process involving the
oxidation by micro-organisms of the nutrients present in
the sewage.
Secondary Treatment
Tertiary Treatment:
• Involves chemical and biological processes
• Involves the removal of phosphates (household
detergents) and nitrates (organic materials) from
the effluent resulting from secondary treatment
• Remember nitrates and phosphates cause
pollution by eutrophication
• Phosphates removed by precipitation. Reacted
with a compound such as aluminium sulphate
producing an insoluble salt – aluminium
phosphate. Other additives used are iron(III)
chloride and lime. Insoluble phosphate compounds
allowed to settle before effluent discharge.
• Nitrates present in the form of ammonia,
nitrite compounds, nitrate compounds or
organic compounds containing nitrogen.
• Nitrates removed by biological denitrification.
Bacteria is used to reduce nitrates to nitrogen
gas. The removal of all nitrogen compounds can
be very difficult and quite expensive.

Effluent may now be discharged into waterways!!!

Definition:
Tertiary treatment involves the removal of phosphates
and nitrates from the effluent
 Instrumental
Methods of
Water Analysis
A) pH meter

B) Atomic Absorption Spectrometry

C) Colorimetry

*Notes on separate handout*

Mandatory Experiment: To estimate the concentration
of free chlorine in swimming pool water or bleach using
a comparator

Must understand:
- theory of experiment

Student Questions:

Book – pg.290 No’s 19.11-19.12

Workbook – pg.49 W19.9