PHYSICO-CHEMISTRY

AND QUALITY OF WATER

Master in Water Engineering

Unit 2. BASICS CONCEPTS OF

CHEMISTRY

Dra. Ana Vázquez González

1
 INDEX
Ponderal´s laws of chemistry:
•Law of defined proportions
•Law of multiple proportions
Molecular weight, mol, Avogadro´s number
•Stoichiometry of reactions
•Units of concentration:
•Molarity, molality, normality, molar fraction, % in
weigtht, % in volume, Total disolved Conductivity
•pX
•hardness
•Alkalinity, Acidity

2
 PONDERAL LAWS

PONDERAL LAW OF DEFINED PROPORTIONS

When two elements are combined to form a

compound, they do it in a fixed weight ratio

3
Example of LAW OF DEFINED PROPORTIONS

Sulfur, oxygen and zinc form

zinc sulfate in a ratio S: O: Zn 1:1.99:2.04.
Find: a) % in weight of zinc sulfate;
b) The amount of sulfate that can be obtained if we
have 8.53 g of zinc

1+1.99+2.04=5.03

5.03 100 5.03 100 5.03 100

  
1 S 1.99 O 2.04 Zn

S= 19.88 % 40.56 gcinc 8.53

O = 39.56 %  X=21.3 g ZnSO4
100 gsulfato x
Zn = 40.56 %

4
 PONDERAL LAWS

LAW OF MULTIPLE PROPORTIONS

The quantities of material from an element that

is combined with a fixed amount of another
element to form different compounds does so in
a simple ratio of whole numbers

5
EXAMPLE LAW OF MULTIPLE PROPORTIONS

Oxygen + copper  copper oxide (a)

1,00 g 3,971 g

Oxygen + copper  copper oxide (b)

1,00 g 7.942 g

3,971 1

7,942 2
6
 MOLECULAR WEIGHT

According to the law of defined proportions, the

molecules are composed of a fixed number of

atoms of a particular series of chemical elements

7
 MOLECULAR WEIGHT

How do we determine the molecular weight ?

The molecular formula of water is H2O

Pm= 1,008·2+16= 18,008 uam

For every atom of oxygen there will be 2

atoms of hydrogen

8
 VIII
IA A
1A 8A
17
1 2 13 14 15 16 2
VII
1 H IIA IIIA IVA VA VIA
A He
1.008 2A 3A 4A 5A 6A 4.003
7A
3 4 5 6 7 8 9 10
2 Li Be B C N O F Ne
6.941 9.012 10.81 12.01 14.01 16.00 19.00 20.18

7 8 9 10
11 12 3 4 5 6 11 12 13 14 15 16 17 18
VII
3 Na Mg IIIB IVB VB VIB
B ------- VIII ------- IB IIB Al Si P S Cl Ar
22.99 24.31 3B 4B 5B 6B ------- 8 ------- 1B 2B 26.98 28.09 30.97 32.07 35.45 39.95
7B
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
4 K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.88 50.94 52.00 54.94 55.85 58.47 58.69 63.55 65.39 69.72 72.59 74.92 78.96 79.90 83.80

37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
5 Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 (98) 101.1 102.9 106.4 107.9 112.4 114.8 118.7 121.8 127.6 126.9 131.3

57
55 56 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
La
6 Cs Ba Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.9 137.3 * 178.5 180.9 183.9 186.2 190.2 190.2 195.1 197.0 200.5 204.4 207.2 209.0 (210) (210) (222)
138.9

89
87 88 104 105 106 107 108 109 110 111 112 114 116 118
Ac
7 Fr Ra Rf Db Sg Bh Hs Mt --- --- --- --- --- ---
(223) (226) ~ (257) (260) (263) (262) (265) (266) () () () () () ()
(227)

58 59 60 61 62 63 64 65 66 67 68 69 70 71
Serie de los Lantánidos
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
(*) 140.1 140.9 144.2 (147) 150.4 152.0 157.3 158.9 162.5 164.9 167.3 168.9 173.0 175.0

95
90 91 92 93 94 96 97 98 99 100 101 102 103
A
Serie de los Actínidos (~) Th Pa U Np Pu Cm Bk Cf Es Fm Md No Lr
232.0 (231) (238) (237) (242) m (247) (247) (249) (254) (253) (256) (254) (257)
(243)
9
What is the relation between uam
and gr?

The answer: MOL

10
 MOL
What is a mol?
IUPAC (International Union of Pure and Applied
Chemistry):
mol is the amount of substance that there is in a
system which contains as many elementary entities as
there are atoms in 12 g of carbon-12
This quantity is the number of Avogadro:
6.02214 × 1023

Number of Avogadro : Is the number of molecules

that there are in a molar volumen.
Molar volume of the sustance: Is the volume
occupied by a mole of the substance
11
 EL MOL

1 mol ~ PM (g) ~ 6.023x1023 molecule/atom

1 mol H2O ~ 18,008g H2O ~ 6.023x1023 molecule

12
 EXAMPLE

How many mols of H2O are there in 1 kg of

water
PAH= 1.0079 g mol-1 PAO= 15.9994 g mol-1 PAH2O= 18.0152 g mol-1

So, in 1000g of water will be exactly:

1 mol H 2 O
1000g H 2 O   55.509 mols of H 2 O
18.0152g H 2 O

13
 EXAMPLE

How many atoms are there in 200 grams of

water?
PAH= 1.0079 g mol-1 PAO= 15.9994 g mol-1 PMH2O= 18.0152 g mol-1

6,023·10 23 át 1mol
200 g· ·  6,69·10 24 át
1mol 18 g
or
23
6 , 023 ·10 át
200 g ·  6 , 69 ·10 24
át
18 g
14
 EXAMPLE

How many mols of calcite (CaCO3) are there in

1000 g of this sustance?
PACa= 40.08 g mol-1 PAC= 12.011 g mol-1 PAO= 15.9994 g mol-1

PMCaCO3=40.08 + 12.011 + 3x15.9994 = 100.0892 g mol-1

So, in 1000 g of calcite will be, exactly:

1 mol calcite
1000g calcite   9.9911 mols of calcite
100.0892g calcite

15
 EXAMPLE

What is the volume of 1000 g of calcite (CaCO3)?

36.934 cm 3 mol 1 calcite

9.9911 mol calcite   369.011 cm 3 calcite
1 mol calcite

16
THE LAW OF CONSERVATION OF MASS
OR LAVOISIER´S LAW

In a chemical reaction, the material is neither

created nor destroyed, only rearranged.

The total weight of the reactants is equal to

the total weight of the resultant substances
(products)

Lavoisier law is the basis of the chemical

equation.

2 H2 + O 2  2 H2O
17
 ESTOICHIOMETRY
Jeremias B. Richter was the first person to lay down the
principals of the stechiometrics in 1792:

The stoichiometry is the science of measuring the

quantitative proportions or mass ratios by which
chemical elements are associated with each other.
That is, the method using balanced chemical
equations ('balanced') to calculate the quantities of
products or reactants in a chemical reaction.
The fundamental concept of stoichiometry is the
ratio mol: mol

2 NO + O2 → 2 NO2

18
 STOICHIOMETRY

2 HNO3 + Ca(OH)2  Ca(NO3)2 + 2 H2O

When we balance the reaction , What kind

of information does it give us?
The proportions between products and
reactives

What kind of information can we obtain

from balanced chemical reactions?
molar relations (or ratios)
19
 STOICHIOMETRY
HNO3 + 1/2Ca(OH)2  1/2Ca(NO3)2 + H2O
a b c
H: 1+2a=2c c=1
N: 1=2b b = 1/2
Ca: a= b a = 1/2
O: 3+2a=6b+c
2HNO3 + Ca(OH)2  Ca(NO3)2 + 2H2O

20
 EXAMPLE

If we add water to calcium carbide, Ca C2 , we obtain

Calcium hidroxide and acetylene (ethyne). Adjust
the reaction that we will obtain. Calculate haw
many grams of water we will need to obtain 200
grams of acetylene

CaC2+2H2O Ca(OH)2+C2H2
? 200 g

2molwater 1molC2 H 2 18 g water

200 g C 2 H 2 · · ·  276,92 g water
1molC2 H 2 26 g C2 H 2 1molwater

21
BASIS CONCEPTS

Units of concentration

22
 MOLARITY

Definition
Concentration unit defined as the number of mols
of solute (ni) divided by the number of litres of
solution.

nsolute
M
V( L ) solution

Units: mol L-1 of solution

23
 EXAMPLE

What is the molarity of a solution which contains 25

grams of water in 200 cm3 of solution?

PAH= 1.0079 g mol-1 PAO= 15.9994 g mol-1 PMH2O= 18.0152 g mol-1

1mol ni 1,38
25 g ·  1.38mol M   6,9 mol
18 g V( L ) solution 0,2 L

24
 MOLALITY
Definition
Unit of concentration, defined to be equal to the
number of mols of solute (ni) divided by the
number of kilograms of solvent (ww). .

ni
mi 
1 kg H 2O
Units: mol kg-1 H2O

Water is the most common solvent

25
 EXAMPLE

To calculate the molality of a solution in which

35 grams of Na (OH) is dissolved in 200 g of
solvent

35
ni   0,875moles
40
0,875moles
m  4,375 mol
0,2 Kg kg

26
 MOLALITY AND MOLARITY

From the analytical point of view, the molar scale is

more practical than molal.

However, the molal scale is preferable to molar

scale for thermodynamic calculations, because it
is independent of the effects of temperature and
concentration of solutes on the density of the
solution

. 27
 MOLALITY AND MOLARITY

In any case, when the solutions are diluted and for

ambient temperatures, both concentration scales

are ‘almost’ equivalent from the numerical point of

view

28
 Normality
Definition

Normality is a measure of concentration equal to the

gram equivalent weight of solute (ni) per litre of
solution. Gram equivalent weight is the measure of the
reactive capacity of a molecule.

equivalentssolute mg / L
N N
Lsolution Eq.Wt.

mass
equivalent 
Eq.Wt
29
 EQUIVALENTS IN WEIGHT
There are 3 diferentes ways to calculate the equivalents in
weight:

The charge of the ion

1 mol Ca+2  2 mol charges  2 eq

Number of H+ or OH- produced in an acid/base reaction

1 mol H+  1 mol charge  1 eq

Number of e- produced in a redox reaction:

1 mol e-  1 mol charge  1 eq

30
1. Equivalents in weight according to the charge
of the ion
molecular weight
equivalent weight 
ch arg e of ion

2. Equivalents in weight for acid/base reactions

molecular weight
equivalent weight 
n º of H  or OH 

3. Equivalents in weight for redox reactions

molecular weight
equivalent weight 
n º of electrons

31
 EQUIVALENTS IN WEIGHT

For the calculation of the normality, e- have

preference over the H+ and OH- in those
reactions that involve them simultaneously

32
 EXAMPLE
What is the normality of a solution that
contain 60 mg/L of CO3-2?

mg / L molecular weight
N equivalent weight 
Eq.Wt. ch arg e of ion

60.0092 g CO32 / 1 mol CO32

P.E.CO 2  2
 30.0046 g / eq
3
2 equivalents / 1 mol CO 3

60 mg CO32 / 1 L
N  2 meq / L
30.0046 mg / meq

33
 EXAMPLE

What is the normality of a solution that contain

49 mg/L of H2SO4?
mg / L molecular weight
N equivalent weight 
Eq.Wt. n º of H  or OH 

98.07948 g H 2 SO4 / 1 mol H 2 SO4

P.E.H 2 SO4   49.09374 g / eq
2 equivalents / 1 mol H 2 SO4

49 mg H 2 SO4 / 1 L
N  1 meq / L
49.09374 mg / meq
34
 EXAMPLE
What is the equivalent in weight of the oxygen in this
reaction if the solution contain 6 mg/L of O2.? What
is the normality?
O2 + 4H+ + 4e- = 2 H2O ?

mg / L molecular weight
N equivalent weight 
Eq.Wt. nº of electrons

31.9988 g O2 / 1 mol O2
equivalent weight   8 g O2 / eq
4 equivalents / 1 mol O2

6 mg O2 / 1 L
N  0.75 meq / L
7.9997 mg / meq
35
 MOLAR FRACTION
Definition
The molar fraction of a solution component Xi is the
fraction of moles of component i of the total number of
moles of all components in solution

This is an adimensional magnitude Xi 

ni
n
 nj
j1
XNaCl + Xwater = 1.

The sum of the mole fractions for a solution will be

equal to 1. 36
 MOLAR FRACTION

What is the molar fraction of each component in a solution

with 3.57 g of sodium chloride, NaCl, dissolved in 25.0 g of
water?
Solution

1) convert from mass of NaCl to moles of NaCl.

2) Convert from mass of water to moles of water.
3) Substitute these two quantities into the defining equation
for mole fraction.

37
QUANTITIES RELATIED

Fraction in weight
%, ‰ , ppmw, ppbw, pptw

wi
% wi  n  100
w
j 1
j

38
 OTHER MEASUREMENTS

Fraction in volume

%, ‰ , ppmv, ppbv, pptv

Vi
%Vi  n  100
V
j 1
j

39
 EXAMPLE

If we dissolve 20g of KClO3 in 500 g of water. What is

the % in weight? And what is the molar fraction?

g KClO3 20
% weight  ·100  ·100  3,84%
g tot 520
PM KClO3=39,10+35,45+16·3=122,55 g/mol
PM H2O=1,008·2+16=18,016 g/mol

20
122,55
X KClO3   5.83·10 3
20  500
122,55 18

40
 TDS
(TOTAL DISSOLVED SOLIDS)
Definition

Is the sum of the total weight of the solutes that

there are present in a solution (after filtering the
sample).

Units: mg/Kg, mg/L

41
TOTAL DISSOLVED SOLIDS (TDS)

Attention

When TDS are in excess of 7000 mg/L, it will

be necessary to consider the density of the
solution to change the concentrations in
volumen (M, mg/L, etc.) to concentration in
weight (m, ppmw, etc.)

42
 CONDUCTIVITY-TDS

 Electrical Conductivity (EC) is the messure of the

capacity that a solution has to conduct energy.
 TDS and electric conductivity are closely related.
 The greater the amount of dissolved salts in the
water, the greater the value of electrical
conductivity
 Water temperature affects electrical
conductivity so that its value increases by 2 to
3% for each degree Celsius increase in
temperature

TDS (mg/L) = 0.5 x 1000 x EC (µS/cm)

43
 PX
Generally used to indicate the negative value of the
logarithm (decimal) of the molar concentration of the
species X

Symbol: pH, pK, pCl, ...

pX = -log10[X]

pK = -log10[K]

44
 PH
 The pH is related to the concentration of
protons in water. pH is defined as:

pH   logH  
 Water with pH < 7: acid water
 Water with pH > 7: basic water

 The pH is a very important factor, because

certain chemical processes can only take place at
a certain pH.

45
 HARDNESS

 Hardness is a chemical characteristic of water

that is determined by the content of carbonates,
bicarbonates, chlorides, sulfates and nitrates
occasionally calcium and magnesium.

 Hardness: It is expressed as mg CaCO3 /L

46
 TYPES OF HARDNESS

 Temporary hardness (Carbonate hardness): It is

determined by the content of carbonates and
bicarbonates of calcium and magnesium.

 Permanent hardness (hardness not due to

carbonates): It is determined by salts of calcium
and magnesium except carbonates and
bicarbonates.

47
 HARDNESS

hardness (mg CaCO3 /L) Clasification

0-100 Soft

101-200 moderately hard

200-300 Hard

>300 very hard

48
 HARDNESS
Calculations for total hardness : Expressed as ppm of
CaCO3

mg/l of total hardness = [ meq/L (Ca+2 y Mg+2)]x 50

Calculations for hardness of Calcium : Expresed as ppm of

CaCO3

mg/l hardness of calcium = (meq/L Ca+2) x 50

Calculations for hardness of Magnesium : Expressed as ppm

of MgCO3

mg/l hardness of magnesium = (meq/L Mg+2) x 50

49
 HARDNESS
Calculate the hardness of water that contains
1.73 meq/l de Ca+2

meq 100 mgCaCO 3

1.73 *  86.5mg / l
l 2meq
Soft Water

50
 ALKALINITY
Water alkalinity is the sum of the concentrations of carbonate ions
(CO32-) bicarbonate (HCO3-) and hydroxides (OH-) where the latter is
negligible compared to the rest

Alkalinity due to carbonates and bicarbonates, is represented by TA

(Total Alkalinity) and alkalinity that includes hydroxides, is
represented by TAC (Complete Alkalinity Titration)

These species occur in a water having the effect of a proton buffer

maintaining the pH at a stable level

The alkalinity is expressed in terms of mg/L of calcium carbonate

(CaCO3)

51
 ALKALINITY

The Alkalinity of natural waters is usually due to

carbonates and bicarbonates of calcium, magnesium,
sodium and potassium in some cases is due to, a lesser
extent, borates, silicates and phosphates.

Bicarbonate is the component that contributes to

alkalinity.

Alkalinity gives an index of the resistance of water to

the lowering of pH when acid is added.

52
 ALKALINITY

If a water sample contains 180 mg /L of Ctotal,

expressed as HCO3- What is the concentration
when it is expressed as CaCO3?

gHCO3 12 gC 100 gCaCO3

0.18  
  0.29 gCaCO3 l
l 61gHCO3 12 gC

53
 ACIDITY

Acidity refers to the presence of substances in

water dissociable generating H3O +, such as strong
acids, weak acids and average force, and also the
presence of certain metal cations Fe (III) and Al
(III)

54