Engineering Chemistry

Winter Semester
2021–22

Instructor: Dr. Vivek K. Yadav

VIT Bhopal
[email protected]
Ph: 9452266088
Syllabus Structure

Impurities of Industrial and

water and its Conducting
treatment polymers

Phase equilibria
Energy sources
and Alloys

Energy
Electrochemistry
conversion and
- Corrosion
storage
 Course Plan

• 12-18 sessions

• N Assignments

• M Quizzes

• Practical / Theoretical project

Session 1
 C

D
E
A

Processes?
 Impurities In Water

Physical • Suspended Impurities

Impurities • Colloidal Impurities

• Bacteria
Bacteriological • Algae
Impurities • Fungi

• Dissolved Gases
Chemical • Dissolved Organic Salts
Impurities • Dissolved Inorganic Salts
US Department of the Interior
 Impurities In Water

Physical • Suspended Impurities

Impurities • Colloidal Impurities

• Bacteria
Bacteriological • Algae
Impurities • Fungi

• Dissolved Gases
Chemical • Dissolved Organic Salts
Impurities • Dissolved Inorganic Salts
Water Hardness
• Hardness of water refers to the quantity of dissolved salts of certain
metal ions in water that reduces the tendency to form lather with soap.
• Hard water is “hard” to form lather or foam with.

?
Causes of Water Hardness

• Calcium (Ca2+ ) and Magnesium (Mg2+) ions.

CaCO3 CaCl2
MgCO3 MgCl2
Ca(HCO3)2 CaSO4
Mg(HCO3) 2 MgSO4
How do Ca2+ and Mg2+ get into water?

Limestone pavement

Limestone, calcium carbonate,

does not dissolve in pure water,
BUT it does dissolve in acid rain.

CaCO3 + H2CO3 Ca(HCO3)2

Carbonic
Ca2+
Calcium
Calcium Acid (acid Hydrogen
carbonate rain) carbonate HARD
Types of rocks across India. Water types?

• Hard water
• Soft water
Differences b/w Soft and Hard Water

Hard water Soft water

Does not produce lather with soap Produces lather with soap

Contains dissolved calcium and Does not contains dissolved

magnesium salts calcium and magnesium salts.

Cleansing action of soap is Cleansing action of soap is not

suppressed suppressed

Requires more material and time Does not require excess material
and time
Temporary hardness
Causes: Calcium hydrocarbonate – Ca(HCO3)2
Magnesium hydrocarbonate – Mg(HCO3)2

Removal: boiling the water

Ca(HCO3) 2 → CaCO3 + H2O + CO2
Mg(HCO3)2 → Mg(OH)2 + 2 CO2

Permanent hardness
Causes: chlorides and sulphates of Ca2+, Mg2+, Fe3+
e.g. CaCl2, MgSO4

Removal: not by boiling the water

Sophisticated water treatment methods
 Disadvantages of Hard Water
Scale Formation
• CaCO3 formed upon boiling water with temporary hardness, is NOT soluble in
water.
• This calcium carbonate precipitates out, coating the insides of boilers, kettles,
pipes etc.

It reduces the efficiency of any heating element, using more energy.

It can block pipes and damage equipment. Expensive to remove.
 Disadvantages of Hard Water
Sludge Formation
• Salts such as MgCl2, CaCl2, MgCO3, MgSO4 etc. have higher solubility in hot
water than cold water.
• Get deposited in the ”cold” part of boilers.
• Soft and loose precipitates.

Poor conductor of heat. Can combine with scale formation.

Removed by wire brush.
 Disadvantages of Hard Water
Soap Scum Formation
• Calcium and magnesium ions react with soap to make calcium and magnesium stearate.
2 C17H35COONa + CaCl2 → (C17H35COO)2Ca + 2 NaCl
(Sodium stearate) (calcium stearate)

2 C17H35COONa + MgSO4 → (C17H35COO)2Mg + Na2SO4

(Magnesium stearate)

Lather is only formed once all the Ca2+ /Mg2+ ions have been precipitated.
Less bubbles, more soap!!!
 Advantages of Hard Water

Some people still prefer it! Can you think of any reasons why?

v Taste: some people prefer it

v It’s good for your teeth and bones (Calcium ions)
v It can protect against heart problems
v It prevents the poisonous lead dissolved in drinking water.
 Degree of Hardness
Hardness is expressed in terms of equivalence of CaCO3: highly insoluble
(easy for precipitation) and molecular weight of 100 (easier calculation).

For a particular hardness producing substance, say X,

Strength of X (mg/L) x 50

CaCO3 Equivalent =
Chemical equivalent of X

NOTE: There may be no Calcium carbonate in the sample at all!!! But we are
expressing it as an equivalence.
Example: Find multiplication factor for converting into CaCO3 equivalents for
following salts and ions?

Ca(HCO3)2 CO2
Mg(HCO3)2 HCO3-
CaSO4 OH-
CaCl2 CO32-
MgSO4 H+
MgCl2 Mg(NO3)2
CaCO3 NaAlO2
MgCO3 FeSO4

Ca (HCO3)2 = 40 + 2 (1 + 12 + 48) = 162

100 / 162 = 50 / 81
Example: Find multiplication factor for converting into CaCO3 equivalents for
following salts and ions?

Ca(HCO3)2 50/81 CO2 50/22

Mg(HCO3)2 50/73 HCO3- 50/61
CaSO4 50/68 OH- 50/17
CaCl2 50/55.5 CO32- 50/30
MgSO4 50/60 H+ 50/1
MgCl2 50/47.5 Mg(NO3)2 50/74
CaCO3 50/50 NaAlO2 50/82
MgCO3 50/42 FeSO4 50/76

Na = 23, Mg = 24, Al = 27. S = 32, Ca = 40, Fe = 56

Units of Hardness
1 ppm = 1 part by weight of CaCO3 1 mg/L = 1 mg of CaCO3 equivalent
equivalent in 106 parts by weight of in one litre of water.
water.

Part per 1 ppm = 1 mg/L Milligrams

million per litre
(ppm) (mg/L)

1 ppm = 0.1 °Fr Units of

Hardness

Degree Clarke’s
French Degree
(°Fr) (°Cl)

1 °Fr =1 part of CaCO3 equivalent in 1 °Cl = 1 part of CaCO3 equivalent in

105 parts of water. 70, 000 parts of water.
Degree of Hardness

Hardness Level ppm

Soft 0 - 17
Slightly Hard 17 - 60
Moderately Hard 60 - 120
Hard 120 - 180
Very Hard 180 and above

Source: Water Quality Association (WQA)

Example: A water sample contains 150 mg of CaSO4 per litre. Calculate the
hardness?

Answer:
Chemical equivalent of CaSO4 = 68

150 x

50
CaCO3 equivalent = mg/L = 110.29 mg/L
68
 AAS analysis of a water sample determined the Ca2+ hardness to be 36 mg/L and the
Mg2+ hardness to be 16 mg/L. What is the total hardness expressed as CaCO3
equivalents?

36 mg Ca2+ * 50 g CaCO3 = 90 mg/L as CaCO3

20.05 g Ca2+

16 mg Ca2+ * 50 g CaCO3 = 66 mg/L as CaCO3

12.15 g Mg2+

Total hardness = 90 + 66 = 156 mg/L as CaCO3

Calculate hardness of all salts/ions à Type of substance à Type of hardness

How many grams of MgCO3 dissolved per litre gives 124 ppm of hardness?

Strength of MgCO
3 (mg/L) x 50

Hardness =
Chemical equivalent of MgCO3

Strength of MgCO3 = 124 x (MgCO3 equivalence) ppm

CaCO3 equivalence

= 124 x (42/50) ppm = 104.16 ppm

= 104.16 mg/L
Hardness Measurement

• Useful test that provides a measure of the water quality to be

used for household and industrial purposes.

• Measure before having to deal with scale formation.

• EDTA Method
• O. Hehner’s Method
• Soap Titration Method
• Warta-Pfeifer Method
Strategy

• If you are looking for

“hardness”, what are you
actually searching for…?

Metal ions!

• What’s the easiest way to

quantify the amount of
metal ions?

Precipitate them!
EDTA Method

• Complex formation titrations

• Chelating or complexing agent in metal ion titrations is EDTA,

(ethylenediaminetetracetic acid).
• Tetraprotic acid
• Sodium salt of EDTA is used because of its high solubility.
• This causes the water to become softened, but the metal ions are not
removed from the water.
 M2+ + EDTA4- → [ M-EDTA ]2- + 2H+

EDTA, M2+, and M-EDTA are all soluble and colorless. No visible change…

Need a secondary indicator – some visible change.

Indicator:

Erichrome Black T (EBT)

• EBT is a blue colored dye when alone in water and turns red when complexed with a
Metal ion.
• Works at pH 10
• Excess EDTA causes a red to blue color change at near neutral pH.
M-EBT + EDTA ® M-EDTA + EBT
(red) (colorless) (blue)

Eriochrome black T
1st Step: The calcium ion coordinates with the indicator (Eriochrome Black T).

H2In- + Ca2+ ↔ CaIn- + 2H+

2nd Step: The EDTA chelates the calcium ion and releases the indicator.

EDTA (aq) + CaIn–(aq) → HIn2-(aq) + CaEDTA (aq)

EDTA

Water + EBT
Experiment:

• The hard water is buffered to a pH value of approx. 10 using

ammonia buffer and a few drops of EBT are added, thus formed
weak complex of metal ion and EBT has wine-red colour.

• Add EDTA, which first combines with free metal ions and form
colorless metal-EDTA complex. After all ions have been
consumed, next EDTA drops displaces EBT from the metal-
indicator complex. Thus freed EBT changes the solution colour
to blue.

• Total hardness is thus determined:

o MEDTA x VEDTA = MUHW x VUHW

o Strength (gms/L) = MUHW x Molar mass of CaCO3

o Total hardness.
 Hardness Calculation

@B CEF
𝑉>?@A 𝑉CBD
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑆 ×1000 × @B × CEF 𝑚𝑔/𝐿
𝑉CBD 𝑉>?@A

LB CEF
𝑉>?@A 𝑉CBD
𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑆 ×1000 × LB × CEF 𝑚𝑔/𝐿
𝑉MBD 𝑉>?@A

𝑇𝑒𝑚𝑝𝑜𝑟𝑎𝑟𝑦 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 − 𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠

0.28 g of CaCO3 was dissolved in HCl and the solution was made to one litre
with distilled water. 100 ml of the above solution required 28 ml of EDTA
solution on titration. 100 ml of the hard water sample required 35 ml of the
same solution on titration. After boiling 100 ml of this water, cooling and
filtering and then 10 ml EDTA solution was used on titration. Calculate the
temporary and permanent hardness of water.

@B CEF
𝑉>?@A 𝑉CBD
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑆 ×1000 × @B × CEF 𝑚𝑔/𝐿
𝑉CBD 𝑉>?@A

35 100
𝑇𝑜𝑡𝑎𝑙 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 0.28 ×1000 × × = 350 𝑚𝑔/𝐿
100 28

LB CEF
𝑉>?@A 𝑉CBD
𝑃𝑒𝑟𝑚𝑎𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 𝑆 ×1000 × LB × CEF 𝑚𝑔/𝐿
𝑉MBD 𝑉>?@A

10 100
𝑃𝑒𝑟𝑚𝑛𝑒𝑛𝑡 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 0.28 ×1000 × × = 150 𝑚𝑔/𝐿
100 28

𝑇𝑒𝑚𝑝𝑜𝑟𝑎𝑟𝑦 𝐻𝑎𝑟𝑑𝑛𝑒𝑠𝑠 = 350 − 150 = 250 𝑚𝑔/𝐿

 Alkalinity of water
• Hard water is generally associated with high alkalinity.

Alkalinity

CaMg(CO3)2 Ca2+ + Mg2+ + 2CO32-

Dolomitic Hardness
limestone

Hardness and alkalinity generally go hand-in-hand but they are

NOT the same.
 Alkalinity of water
• Alkalinity is defined as the ability to neutralize acids.

• Alkalinity of water is due to the presence of any of the ions

𝑶𝑯W , 𝑪𝑶W𝟐
𝟑 and 𝑯𝑪𝑶 W
𝟑 or mixture of 𝑂𝐻 W
and 𝐶𝑂_
W`
or mixture of 𝐶𝑂_
W`
W
and 𝐻𝐶𝑂_ .

• 𝑂𝐻 W and 𝐻𝐶𝑂_W ions cannot be present together because they combine

by reaction

𝑂𝐻 W + 𝐻𝐶𝑂_W → 𝐶𝑂_W` + 𝐻` 𝑂

• No more than two of the three ions (𝑂𝐻 W , 𝐶𝑂_W` and 𝐻𝐶𝑂_W ) can exist
in the solution.
 Acid-base Titration

• If V1 is the volume of acid used from the start of the titration to the
phenolphthalein end point and V2 is the volume from the
phenolphthalein end point to the methyl orange end point, then the
relation between V1 and V2 for a single component and mixture are
listed in the table below.

Relative Titrant Volume Constituent(s) in the sample

• V2 = 0 OH-
• V1 = V2 CO32-
• V1 = 0 HCO3-
• V1 > V2 OH- and CO32-
• V1 < V2 CO32- and HCO3-
 Estimation of Alkalinity

NHCl x V1, HCl x 50 x 1000

Phenolphthalein Alkalinity, P = ppm
Vw

NHCl x (V1+V2) HCl x 50 x 1000

Total Alkalinity, T= ppm
Vw

Alkalinity due to
Volume (mL)
OH- CO32- HCO3-

V1 = 0 0 0 T

V2 = 0 T 0 0

V1 = V2 0 2P 0

V1 > V2 2P - T 2T - 2P 0

V1 < V2 0 2P T – 2P
50 mL of a water sample required 10 mL of N/50 HCl using methyl orange
indicator but did not give any colouration with phenolphthalein. What is the
type and extent of alkalinity present in the solution?

V1 = 0, V2 = 10 mL

HCO3- only.

NHCl x (V1 + V2) x 50 x 1000

T= ppm
Vw

1/50 x (0 + 10) x 50 x 1000

= ppm
50

= 200 ppm
 100 mL of a water sample required 12 mL of N/50 HCl to phenolphthalein
end point and 15 mL of the acid to methyl orange end point. What is the
type and extent of alkalinity present in the solution?

V1 = 12 mL, V1+V2 = 15 mL

OH- + CO32- only.

NHCl x V1, HCl x 50 x 1000 NHCl x (V1+V2) HCl x 50 x 1000

P= ppm T= ppm
Vw Vw

1/50 x 12 x 50 x 1000 1/50 x 15 x 50 x 1000

P= = 120 ppm T= = 150 ppm
100 100

OH- = 2P – T = 240 - 150 = 90 ppm

CO32- = 2T – 2P = 300 – 240 = 60 ppm

 Boiler Feed Water
• In industries, water is mainly required for cooling and steam generation
purposes.

• Boiler is a heat exchanger which uses radiant heat and hot flue gases, liberated
from burning fuel, to generate steam and hot water for heating and processing
loads.

• Water required to feed in boilers must be of high quality.

If used untreated then it may lead to following problems:

o Scale and Sludge Formation.

o Priming and Foaming
o Boiler Corrosion
o Caustic Embrittlement
Scale And Sludge Formation
• In boilers, water is converted into steam. When water containing impurities is used for
generating steam, the concentration of the dissolved salts increases.
• If dissolved salts takes place in the form of loose, non adherent, slimy precipitates, it is
called sludge.
• If the precipitates form hard, adhering coating on the inner walls of the boilers, it is
called scales.
• Salts responsible for the formation of scales and sludge are CaCO3, CaSO4, Mg (OH)2
MgCl2, and SiO2 etc.
• Sludge can be removed easily but scale formation is more dangerous.
Sludge

Slimy loose precipitate

called sludge suspended
in water

water

Boiler wall

• Sludge is a soft, loose and slimy precipitate formed within the boiler. It can be
easily scrapped off with a wire brush. It is formed at comparatively colder
portions of the boiler and collects in areas of the system, where the flow rate is
slow or at bends.
• It is formed by substances which have greater solubility's in hot water than in
cold water, e.g. MgCO3, MgCl2, CaCl2, MgSO4 etc.,
Sludge
Sludge are formed by the substances having greater solubilities in hot water than in the
cold water e.g. MgCO3, MgCl2, CaCl2, MgSO4 etc.

Disadvantages of Sludge Formation

• Poor conductor of heat so it tends to waste lot of amount of heat. So boilers require more
heat.
• Decrease the efficiency of the boilers.
• Slows down the water circulation as it cause choking of pipes.

Prevention of Sludge Formation

• By using soft water.
• By frequently carrying out the cleaning operations.

Removal of Sludge removed by scrapping off with a brush.

Scale
Causes:
• Decomposition of bicarbonates: When water containing bicarbonates is heated in the
boiler, the bicarbonates present are converted into insoluble CaCO3.
Ca (HCO3)2 à CaCO3 + CO2 + H2O

• Hydrolysis of Mg Salts: Dissolved magnesium salts undergo hydrolysis forming

precipitates of Mg(OH)2.
MgCl2 + 2H2O à Mg(OH)2 + 2HCl

• CaSO4 is less soluble in hot water so it forms hard scale on the heated portions of the
boiler. CaSO4 is the main cause of scale formation in high pressure boilers.

• Silica Salts like calcium silicate, magnesium silicate are completely insoluble in hot
water. So they form hard scale on inner boiler surface and are very difficult to remove.
 Disadvantages:

Heating Heating Scale

H2Ovap H2Ovap

Heating Heating

A boiler without scale A boiler with scale

Wastage of Fuel: Because of low thermal conductivity of the scales, more heat is
supplied to the boiler to maintain the supply of steam leading to wastage of fuels.
 Scale

Disadvantages:

• Bagging: The distortion of boiler material is known as bagging. The

superheating of the boiler leads to the distortion of the boiler material. Due to
overheating, it causes thinning of the boiler material.

• Danger of Explosion: The uneven expansion of the scale may lead to the
cracking of the scale.
Scale
Removal:
• Soft scales are removed with the help of scrapper or wire brush.

• Brittle or hard scales can be removed by giving thermal shocks i.e. heating the
boiler and suddenly cooling with cold water.

• Scales can also be dissolved in certain chemicals and hence can be removed
along with water.
For e.g. CaCO3 scales can be dissolved by using 5-10% HCl. Similarly
EDTA can also be used to dissolve the salts of Ca, with which it forms soluble
complexes.