Chapter 1 Week2

FA-Chap1 (continue) 1
CHAPTER 1
REMIND THE BASIC KNOWLEDGES
REQUIRED FOR ANALYTICAL CHEMISTRY
Contents
 Solutions – Concentrations
 Stoichiometry
 Chemical reactions
 Mass action law
 Equivalent action law

Solutions
 Dilute solution
 Concentrated solution
 Unsaturated
 Saturated
 Supersaturated
Concentration
 Concentration is a general measurement unit stating the

amount of solute present in a known amount of solution
•We can extend their use to gas-phase and solid –phase

samples as well.
Solutions - Concentrations
 Molarity (CM)
 Molality (Cm)
 Mole fraction (CNi)
 Normality (CN)
 Mass per volume (Cg/L)
 Titre (T)
 Solubility (S)
 Percent concentration (C% : w/w; v/v; w/v)
 Parts per Million/Billion/Trillion (ppm, ppb, ppt)
 p-Functions or p-value
• Solubility (S)
• - The amount of a solute (g) in a given amount of a
solvent (100 g), to give a saturated solution, under
specified to and p.
• Mass concentration (Cg/L)
– the amount of solute (g) in 1 liter of solution.
m( g ) m( mg ) m( g )
C( g / L ) = = = 103
V( L ) V( mL ) V( mL )
• Titre (T)
– the amount (g or mg) solute in 1 mL of solution.
m m
Tg / ml = or Tmg / ml = 1000
V V
• Molarity (mol/L or M) or Molar concentration
– Total number of moles of a solute in 1 L of the solution.
m( g )
mol M ( g / mol ) m( g ) 103
CM = = 3
= 
L V( mL ) 10 M ( g / mol ) V( mL )
m( mg )
mol mmol M ( mg / mmol ) m( mg ) 1
CM = = = = 
L mL V( mL ) M ( mg / mmol ) V( mL )
• Molaliry (Cm)/ molal concentration
– number of moles solute in 1000 g of solvent (mol/kg).

- It does not change with temperature.
(q – the amount of solvent (g)
m( g ) 1000
Cm = 
M ( g / mol ) q( g )
• Mole fraction (Ni)
- The mole fraction of a substance is the fraction of all of its
molecules (or atoms) out of the total number of molecules
(or atoms).
• Normality or normal concentration (CN)
- the number of equivalents of solute per liter of solution (N)
wt (g)
number of equivalents (eq) = = normality  volume(L)
g
eq. wt ( )
eq
formula wt ( M )
equivalent weight (EW) =
n
• n: the number of reacting units, depends on the chemical reaction
• Formula weight (M): the mass of a compound containing 1 mole
• Percent concentration (C %):
- the units of solute present in 100 units of solution.

m m
Weight percent C% (m/m): C%( m / m ) = 100 = 100
mq V .d
VX
Volume percent C% (v/v): C%( v / v ) =  100
V
Weight-to-volume percent C% (m/v): m

C%( m / v ) =  100
V
• Part per million (ppm)
• Part per billion (ppb)
• ppm: The units of solute in 106 units of solution.
• For very dilute solutions, it is convenient to express
concentration in ppm or ppb/ppt
• approximation: the density of dilute solution= dH2O= 1.00 g/mL.
masssolute
C ppm =.
 106 ( ppm)
masssolution
Solid solute/solid soln.: 1 ppm = 1 mg/kg = 1 mg/g.

Liquid solute/liquid soln.: 1 ppm = 1 mL/L = 1 nL/mL
Solid solute/liquid soln.: 1 ppm = 1 mg/L = 1 mg/mL.
Solutions and their Concentrations

• Part per billion (ppb)
• The grams of solute in 109 grams of solution.
• For very dilute solutions, it is convenient to express
concentration in ppm or ppb
• approximation: the density of dilute solution= dH2O= 1.00 g/mL.
masssolute
C ppm =.
 106 ( ppm)
masssolution
Solid solute/solid soln.: 1 ppb = 1 mg/kg.

Liquid solute/liquid soln.: 1 ppb = 1 nL/L = 1 pL/mL
Solid solute/liquid soln.: 1 ppb = 1 mg/L = 1 pg/mL.
Density and Specific Gravity of Solutions
•
Density and Specific Gravity of Solutions

Converting between concentration units
C N = CM  n
C g / L = CM  M = C N .Đ = C% .10.d
Solutions and their Concentrations

• p-functions or p-values
• The p-value is the negative log (base 10) of the molar
concentration
• p-values are convenient to use when changes occur over

several orders of magnitude
 [H+], pH
 [Ba2+], pBa
 [Cl-], pCl
Law of equivalent action
In a certain reaction, numbers of equivalent of

reactants are equal.
V1.C1 = V2.C2
→ applied to quantitative determination

PREPARING SOLUTIONS
• The most common activity in any analytical lab.
• Pipets and volumetric flasks: be exact.
• Graduated cylinders, beakers and reagent bottles: be
approximate.
Apparatus are Commonly used in Preparation of

Solution
PREPARING SOLUTIONS
1. Preparing Stock Solutions
o A stock solution is prepared by weighing out an appropriate
portion of a pure solid or by measuring out an appropriate volume of
a pure liquid and diluting to a known volume.
o Exactly how this is done depends on the required concentration
unit.
2. Preparing solutions by dilution
• the total amount of solute is the same before and after dilution.
• Law of dilution
Cconcentrated.Vconcentrated = Cdilute. Vdilute
Stoichiometry
Stoichiometric calculations
• Conservation of Mass principle
• An element’s total mass at the end of a reaction must be
the same as that present at the beginning of the reaction
(except for nuclear reaction)
• Eg. Unbalanced reaction:
• Reaction unit: C
• Reaction unit: H
• Eg 2. NH4+  Fe(NH4)2(SO4)2.6H2O
• Reaction unit: NH4+
• Conservation of Charge principle
• The total cation charge and the total anion charge in the
precipitate is equal.
• The reaction units are the absolute values of the charges
on the cation and anion that make up the precipitate.
• Eg. Unbalanced reaction: Ca2+ + PO43-  Ca3(PO4)2↓

2 x moles Ca2+ = 3 x moles PO43-
• Conservation of Protons principle
• Acid-base reaction: the number of protons be donated to
the base or the number of protons the base can accept
from the acid.
• Note: For an acid, the number of reaction units depends on how
many of the protons are capable of reacting with the chosen base
(not how many acidic protons).
Eg.
• Conservation of Electron Pairs principle
• In a complexation reaction, the reaction unit is an electron
pair.
• For the metal, the number of reaction units is the number of
coordination sites available for binding ligands.
• For the ligand: the number of reaction units is equivalent to the
number of electron pairs that can be donated to the metal.
• Special case: ligand EDTA (ethylenediaminetetracetic
acid) can donate 6 electron pairs and 6 coordinate metal
ions, such as Cu2+, thus:
• Conservation of Electrons principle
• In a redox reaction:
• For reducing agent: number of electrons released during its
oxidation.
• For oxidizing agent: the number of electrons needed to cause its
reduction.
Eg. Fe3+ + oxalic acid

• Conservation of Mass principle
• An element’s total mass at the end of a reaction must be
the same as that present at the beginning of the reaction
(except for nuclear reaction)
• Eg. Unbalanced reaction:
• Reaction unit: C
• Reaction unit: H
• Eg 2. NH4+  Fe(NH4)2(SO4)2.6H2O
• Reaction unit: NH4+
• Conservation of Charge principle
• The total cation charge and the total anion charge in the
precipitate is equal.
• The reaction units are the absolute values of the charges
on the cation and anion that make up the precipitate.
• Eg. Unbalanced reaction: Ca2+ + PO43-  Ca3(PO4)2↓

2 x moles Ca2+ = 3 x moles PO43-
• Conservation of Protons principle
• Acid-base reaction: the reaction unit is the proton, the
number of protons be donated to the base or the number
of protons the base can accept from the acid.
• Eg. Unbalanced reaction: NaOH + H3PO4 
• H3PO4 can donate all its 3 protons to NaOH whereas the strong
base NaOH can accept one proton.
3 x moles H3PO4 = 1 x moles NaOH
Note: For an acid, the number of reaction units depends on how many
of the protons are capable of reacting with the chosen base (not how
many acidic protons).
Eg.
A conservation of protons requires that:
• Conservation of Electron Pairs principle
• In a complexation reaction, the reaction unit is an electron
pair.
• For the metal, the number of reaction units is the number
of coordination sites available for binding ligands.
• For the ligand: the number of reaction units is equivalent
to the number of electron pairs that can be donated to the
metal.
• Special case: ligand EDTA (ethylenediaminetetracetic
acid) can donate 6 electron pairs and 6 coordinate metal
ions, such as Cu2+, thus:
• Conservation of Electrons principle
• In a redox reaction: the reaction unit is an electron transferred from a
reducing agent to an oxidizing agent.
• For reducing agent: number of electrons released during its oxidation.
• For oxidizing agent: the number of electrons needed to cause its
reduction.
• Eg. Fe3+ + oxalic acid
• Fe3+ undergoes a 1-electron reduction.

• Each C atom in oxalic acid is initially present in a +3 oxidation
state, whereas the C atom in CO2 is in a +4 oxidation state. Thus,
we can write:
• Note: moles of oxalic acid are multiplied by 2 since there are 2 C
atoms, each of which undergoes a 1-electron oxidation.
Chemical equilibrium
(1)
aA + bB dD + eE
(2)
 In fact, most of the reactions are reversible.

 Dynamic equilibrium → reactants and products.
Chemical equilibrium
• Reversible reaction
(1)
aA + bB dD + eE
(2)
• Equilibrium constant, K
d e
K1 =
 D   E 
• Ionic solution, Ion force m ≠ 0
 Aa  B b
• Ion force m=0

K1 =
D   E 
d e
Aa  Bb
Law of mass action

For a steady state of dynamic chemical equilibrium at a
given temperature and pressure in a reversible
reaction, the ratio of the product of equilibrium
concentrations of the end products of the reaction
to the product of equilibrium concentrations of the
initial products of the reaction is a constant value.
K1 =
D   E 
d e
= constant
A  B
a b
 applicable only to non-electrolytes and weak electrolytes in

dilute aqueous solutions
Law of mass action
K1 =
D   E 
d e
= constant
A  B
a b
Dynamic equilibrium → Le Châtelier Rule.
K >1
K > 107: complete! quantifiable!

Chapter 1 Week2

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Chapter 1 Week2

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FA-Chap1 (continue) 1

 Mass action law

 Equivalent action law

 Concentration is a general measurement unit stating the

•We can extend their use to gas-phase and solid –phase

– the amount of solute (g) in 1 liter of solution.

– the amount (g or mg) solute in 1 mL of solution.

– number of moles solute in 1000 g of solvent (mol/kg).

- the units of solute present in 100 units of solution.

Weight-to-volume percent C% (m/v): m

Solid solute/solid soln.: 1 ppm = 1 mg/kg = 1 mg/g.

Solutions and their Concentrations

Solid solute/solid soln.: 1 ppb = 1 mg/kg.

Density and Specific Gravity of Solutions

Density and Specific Gravity of Solutions

Converting between concentration units

Solutions and their Concentrations

• p-values are convenient to use when changes occur over

Law of equivalent action

In a certain reaction, numbers of equivalent of

→ applied to quantitative determination

Apparatus are Commonly used in Preparation of

• Eg. Unbalanced reaction: Ca2+ + PO43-  Ca3(PO4)2↓

Eg. Fe3+ + oxalic acid

• Eg. Unbalanced reaction: Ca2+ + PO43-  Ca3(PO4)2↓

• Fe3+ undergoes a 1-electron reduction.

 In fact, most of the reactions are reversible.

• Ion force m=0

Law of mass action

 applicable only to non-electrolytes and weak electrolytes in

Law of mass action

Dynamic equilibrium → Le Châtelier Rule.

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