Chem 28 Fundamentals of Analytical Chemistry

Review of Basic Concepts in Analytical Chemistry

 Review of Basic Concepts in Analytical Chemistry
➢ Stoichiometric Concepts
Mole concept
Concentrations
Dilution and aliquot
Stoichiometric calculations
➢ Ionic Equilibria Calculations
Equilibrium states
Equilibrium calculations using systematic approach
Stoichiometric Concepts
 Learning Outcomes
➢ Apply the mole concept for quantitative calculations
➢ Compute concentrations of substances in various ways and units
➢ Apply the concept of dilution in solutions
 Stoichiometric Concepts
➢ Stoichiometry describes the quantitative relationship among the
amounts of reactants and products
➢ We can predict the amount of products formed from the amounts of
reactants available
➢ The limiting reactant is completely used up in the reaction, and we can
predict the amount of product formed from the amount of the limiting
reactant available at the start of the reaction
➢ The excess reactant is not fully consumed in the reaction
 The Mole Concept
➢ The mole is the SI* unit of amount of substance
➢ One mole contains exactly 6.022 140 76 × 1023 elementary entities
(Avogadro number)
➢ The coefficients in a balanced equation can represent the number of
moles of substances needed in a reaction
For a general reaction: aA + bB → cC +dD
𝑐
# 𝑚𝑜𝑙 𝐶 = # 𝑚𝑜𝑙 𝐴 ×
𝑎

𝑐
# 𝑚𝑜𝑙 𝐶 = # 𝑚𝑜𝑙 𝐵 ×
𝑏

* Système International = International System of Units

 The Mole Concept
Example 2-1
How many moles of AgCl(s) are formed when 3.0 moles each of AlCl3 and AgNO3 are
mixed?
Ag+ + Cl− → AgCl(s)
# mol AgCl from 3.0 mol AlCl3:
3.0 𝑚𝑜𝑙 𝐶𝑙 − 1 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙
#𝑚𝑜𝑙 𝐴𝑔𝐶𝑙 = 3.0 𝑚𝑜𝑙 𝐴𝑙𝐶𝑙3 × × −
= 9.0 mol AgCl
𝑚𝑜𝑙 𝐴𝑙𝐶𝑙3 𝑚𝑜𝑙 𝐶𝑙

# mol AgCl from 3.0 mol AgNO3 :

1.0 𝑚𝑜𝑙 𝐴𝑔+ 1 𝑚𝑜𝑙 𝐴𝑔𝐶𝑙

#𝑚𝑜𝑙 𝐴𝑔𝐶𝑙 = 3.0 𝑚𝑜𝑙 𝐴𝑔𝑁𝑂3 × × +
= 3.0 mol AgCl
𝑚𝑜𝑙 𝐴𝑔𝑁𝑂3 𝑚𝑜𝑙 𝐴𝑔

 3.0 mol AgCl are formed, since this is lesser in amount and AgNO3 is LR
 The Mole Concept
SAQ2.1 (3 pts)
How many moles of Ca3(PO4)2(s) are formed when 4.0 moles each of Ca(NO3)2 and Na3PO4
are mixed?
3 Ca2+ + 2 PO43− → Ca3(PO4)2(s)
 Precipitation Reactions

Acids, Bases, and

Aqueous Neutralization Reactions
Solution
Oxidation–Reduction
Chemistry (Redox) Reactions

Complex formation
reactions
Methods of Expressing Concentrations of Solutions Frequently
Used in Analytical Chemistry
➢ Molarity (M)
➢ Analytical molarity (CX) or Formality (F)
➢ Mass % (m/m)
➢ Volume % (V/V)
➢ Mass/Volume % (m/V)
➢ Parts per million (ppm)
➢ Parts per billion (ppb)
➢ Normality (N)
➢ Titer (mg A/mL B)
➢ Density (m/V)
➢ Relative density (d) (specific gravity in older literature)
 Molarity and Analytical Molarity

➢ Molarity (M): moles solute / L solution = mmoles solute / mL solution

 refers to species or equilibrium concentration

➢ Analytical molarity (CX) or Formality (F): total number moles solute regardless of its
chemical state/ L solution = total mmoles solute / mL solution
 refers to analytical or total concentration; describes how a solution of a given
molarity can be prepared
 Molarity and Analytical Molarity
➢ Let’s consider the behavior of three types of solutes when dissolved in water:
 Solutes that dissociate completely into positive and negative ions  strong
electrolytes, e.g. NaCl; in an aqueous solution, there are Na+ and Cl− ions
and no undissociated NaCl
 Solutes that dissociate partially into positive and negative ions  weak
electrolytes, e.g. CH3COOH; in an aqueous solution, there are H+ and
CH3COO− ions and undissociated CH3COOH according to the following
equilibrium reaction
𝐶𝐻3 𝐶𝑂𝑂𝐻 ⇄ 𝐻+ + 𝐶𝐻3 𝐶𝑂𝑂−
 Solutes that do not dissociate into positive and negative ions  non-
electrolytes, e.g. glucose (C6H12O6); in an aqueous solution, there are only
undissociated molecules of C6H12O6
➢ How do we determine the molarity and analytical molarity in these three
types of solutes?
 Molarity and Analytical Molarity in a Solution of a
Strong Electrolyte, e.g. NaCl
➢ When 1.0 mol NaCl is dissolved in enough water to make 1.0 L, then we have 1.0 mol
Na+ and 1.0 mol Cl− and no undissociated NaCl in solution
➢ The solution is therefore 1.0 M in Na+ and 1.0 M in Cl−
1.0 𝑚𝑜𝑙 𝑁𝑎+ 1.0 𝑚𝑜𝑙 𝐶𝑙 −
𝑀𝑁𝑎+ = and 𝑀𝐶𝑙 − =
𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
➢ It is not accurate to describe the concentration as 1.0 M NaCl solution, since there is
no undissociated NaCl
➢ instead we describe the concentration of NaCl based on how the solution was
prepared using analytical molarity:
1.0 𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙 𝑁𝑎𝐶𝑙
𝐶𝑁𝑎𝐶𝑙 =
𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
 Molarity and Analytical Molarity in a Solution
of a Weak Electrolyte, e.g. CH3COOH
➢ When 1.0 mol CH3COOH (or HOAc) is dissolved in enough water to make 1.0 L, and if
x mol of HOAc dissociates, then we have x mol H+ and x mol OAc− and (1.0 – x) mol of
undissociated HOAc in solution
➢ We describe the solution in terms of the species H+, OAc− and HOAc:
𝑥 𝑚𝑜𝑙 𝐻 + 𝑥 𝑚𝑜𝑙 𝑂𝐴𝑐 − (1.0−𝑥) 𝑚𝑜𝑙 𝐻𝑂𝐴𝑐
𝑀𝐻 + = , 𝑀𝑂𝐴𝑐 − = and 𝑀𝐻𝑂𝐴𝑐 =
𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
➢ It is not accurate to describe the concentration as 1.0 M HOAc solution, since it
creates confusion as to whether we are referring to the total HOAc originally placed
in solution or to the HOAc left undissociated in the solution
➢ To avoid confusion, we describe the total concentration of HOAc based on how the
solution was prepared using analytical molarity:
1.0 𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙 𝐻𝑂𝐴𝑐
𝐶𝐻𝑂𝐴𝑐 = = 𝑀𝐻𝑂𝐴𝑐 + 𝑀𝑂𝐴𝑐 −
𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
 Molarity and Analytical Molarity in a Solution
of a Non-Electrolyte, e.g. C6H12O6
➢ When 1.0 mol glucose (C6H12O6) is dissolved in enough water to make 1.0 L solution,
then we have 1.0 mol of undissociated C6H12O6 in solution
➢ The concentration is therefore 1.0 M C6H12O6 solution since only the undissociated
C6H12O6 is in the solution
1.0 𝑚𝑜𝑙 𝐶6 𝐻12 𝑂6
𝑀𝐶6 𝐻12 𝑂6 =
𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
➢ We can also describe the concentration based on how the solution was prepared
using analytical molarity:
1.0 𝑡𝑜𝑡𝑎𝑙 𝑚𝑜𝑙 𝐶6 𝐻12 𝑂6
𝐶𝐶6 𝐻12 𝑂6 =
𝐿 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
➢ Therefore, for a solution of a non-electrolyte, MX = CX
 Molarity and Analytical Molarity
Example 2-2
HNO2 ⇄ H+ + NO2−
A 750. mL aqueous
i CHNO2
solution containing
6.31 g of nitrous acid, c − 0.587 CHNO2 + 0.587 CHNO2 + 0.587 CHNO2
HNO2 (47.0135 e CHNO2 − 0.587 CHNO2 0.587 CHNO2 0.587 CHNO2
g/mol), is about 58.7
% dissociated at 25 1 𝑚𝑜𝑙 𝐻𝑁𝑂2
6.31 𝑔 𝐻𝑁𝑂2 ×
oC. Calculate the 47.0135 𝑔 𝐻𝑁𝑂2
(a) 𝐶𝐻𝑁𝑂2 = = 0.1789 = 0.179 𝑚𝑜𝑙/𝐿
1𝐿
(a) analytical 750. 𝑚𝐿 ×
1000 𝑚𝐿
molarity of
nitrous acid
(b) 𝑀𝐻𝑁𝑂2 = 0.1789 × 1.000 − 0.587 = 0.0739 𝑚𝑜𝑙/𝐿
(b) molarity of HNO2
(c) molarity of NO2− (c) 𝑀𝑁𝑂2− = 0.587 × 0.1789 = 0.1050 = 0.105 𝑚𝑜𝑙/𝐿
 Molarity and Analytical Molarity
➢ We now know the difference between species concentration MX and
analytical molarity (or total concentration or formality) CX
➢ Almost all books use M to also denote CX even for electrolytes
➢ So how do we know if M refers to species concentration or to analytical
concentration?
➢ Most of the time M refers to how the solution was prepared
1.0 M NaCl solution…  M refers to analytical molarity
A solution is 1.0 M in H+…  M refers to species concentration
 Different expressions of percentage (%)

mass solute
Mass % (m/m) = × 100
mass solution

volume solute
Volume % (V/V) = × 100
volume solution

mass solute, g
Mass/volume % (m/V) = × 100
volume solution, mL
 Parts per million (ppm)
𝑚𝑎𝑠𝑠 𝑜𝑓 𝐴
𝑝𝑝𝑚 𝐴 = × 106
𝑚𝑎𝑠𝑠 𝑜𝑓 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
* Let’s derive a practical expression for ppm:
𝑔𝐴 1000 𝑚𝑔 𝐴 1000 𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑚𝑔 𝐴
𝑝𝑝𝑚 𝐴 = 6 × × =
10 𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑔𝐴 𝑘𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑘𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

* Since ppm is a dilute concentration we can assume that the density of an aqueous
solution approaches that of water (≅ 1 g/mL)

𝑚𝑔 𝐴 1 𝑘𝑔 1 𝑔 1000 𝑚𝐿 𝑚𝑔 𝐴
𝑝𝑝𝑚 𝐴 = × × × =
𝑘𝑔 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 1000 𝑔 𝑚𝐿 𝐿 𝐿 𝑎𝑞𝑢𝑒𝑜𝑢𝑠 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

𝑚𝑔 𝐴 𝑚𝑔 𝐴
𝑝𝑝𝑚 𝐴 = ≅
𝑘𝑔 𝑎𝑞𝑢𝑒𝑜𝑢𝑠 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝐿 𝑎𝑞𝑢𝑒𝑜𝑢𝑠 𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛
 Parts per billion (ppb)

mass of A
ppb A = × 109
mass of solution

An equivalent expression for ppb as that for ppm may also be derived:

μg A μg A
ppb A = ≅
kg aqueous solution L aqueous solution
 Density and relative density
➢ Density: mass of a substance per unit volume, e.g. g/mL

➢ Relative density (specific gravity in older literature): ratio of the density

of a substance to the density of water; dimensionless (numerically
equal to density since the density of water is 1 g/mL)
 Sample Problem on Concentrations
SAQ 2.2 (16 pts)
A solution was prepared by dissolving 5.76 g of KCl ∙ MgCl2 ∙ 6H2O (277.85 g/mol) in
sufficient water to give 2.000 L. Calculate
a. the molar analytical concentration of KCl ∙ MgCl2 ∙ 6H2O in this solution
b. the molar concentration of Mg2+.
c. the molar concentration of Cl−.
d. the mass / volume percentage of KCl ∙ MgCl2 ∙ 6H2O.
e. the number of millimoles of Cl− in 25.0 mL of this solution.
f. ppm K+ (39.0983 g/mol).
g. pMg (= -log [Mg2+]) for the solution.
h. pCl (= -log [Cl−]) for the solution.

Skoog et al., Fundamentals of Analytical Chemistry, 9th ed, p 79

 Normality and Titer
➢ Normality (N): # of equivalents solute / L solution

➢ Titer (T): mg A / mL B (mass of species A equivalent to 1 mL of solution B)

 The name of the titer follows from the name of the substance that is
expressed as mg.
 NB = T / EM of A where EM = equivalent mass
 The titer is convenient to use for routine titration of a sample; after
titration, the volume of reagent is multiplied by the titer to obtain the
mass of the sought substance in the titrated sample.

➢ We now need to define equivalent and equivalent mass

 Chemical equivalence, equivalent and equivalent mass
➢ In a titration, the titrant is added until an amount chemically equivalent to the
analyte is reached, and this point is called the equivalence point
➢ At the equivalence point, the number of moles of analyte and titrant may or may not
be equal, but by definition the equivalents of analyte and titrant are always equal
➢ The term equivalent refers to one mole of reacting units
➢ What is a reacting unit?
 In acid-base reaction, it is the H+ furnished by an acid or reacted with by a base
(Bronsted-Lowry definition)
 In redox reaction, it is the number of electrons gained by an oxidizing agent or
lost by a reducing agent
 In precipitate formation and complex formation, it is the valency of the ion
(univalent, divalent, trivalent, etc.)
 Chemical equivalence, equivalent and equivalent mass
➢ Equivalent mass, EM, is the number of grams per equivalent
𝑔
𝐹𝑀 ( )
𝐸𝑀(𝑔/𝑒𝑞) = 𝑚𝑜𝑙
𝑒𝑞
𝑛( )
𝑚𝑜𝑙

where FM = formula mass (or molar mass)

n = # equivalents/mole (value depends on the reaction)

How do we determine the factor n in the following reactions?

1. Acid-base
2. Redox
3. Precipitate-Formation and Complex-Formation
 Calculation of EM in Acid - Base Reactions
Consider the following reactions of H3PO4 and NaOH and determine the amount of H+
donated by the acid or accepted by the base:
Reaction 1: H3PO4 + NaOH → NaH2PO4 + H2O
# mol 1 mol 1 mol
# eq 1 eq 1 eq
n 1 eq/mol 1 eq/mol
EM FM/1 FM/1

Reaction 2: H3PO4 + 2 NaOH → Na2HPO4 + 2 H2O

# mol 1 mol 2 mol
# eq 2 eq 2 eq
n 2 eq/mol 1 eq/mol
EM FM/2 FM/1
EM of H3PO4 depends on the reaction, not on the chemical formula
 Calculation of EM in Redox Reactions
➢ The number of electrons gained or lost may be determined from the change in
oxidation number or from the half reactions
➢ Using the half reactions for the following redox reactions:
Reaction 1: KMnO4 with K2C2O4 in acid medium
Reduction Half reaction: MnO4− + 8 H+ + 5e → Mn2+ + 4 H2O
Oxidation half reaction: C2O42− → 2 CO2 + 2e
 EM of KMnO4 = FM / 5 EM of K2C2O4 = FM / 2

Reaction 2: KMnO4 with KI in neutral solution

Reduction Half reaction: MnO4− + 4 H+ + 3e → MnO2 + 2 H2O
Oxidation half reaction: 2 I− → I2 + 2e
 EM of KMnO4 = FM / 3 EM of KI = FM / 1
EM of KMnO4 depends on the number of electrons gained in a reaction
 EM in Precipitation and Complex Formation
➢ The EM of a participant in a precipitation or a complex formation reaction is that
mass which reacts with or provides one mole of the reacting cation if it is univalent,
one-half mole if it is divalent, one-third mole if it is trivalent, etc.
➢ Therefore the valency of the metal cation (ion charge) determines the number of
equivalents; # of eq anion = # eq cation

Reaction 1 AgNO3 + NaCl → AgCl(s) + NaNO3

Ionic equation Ag+ + Cl− → AgCl(s)
# mol 1 mol 1 mol
# eq 1 eq 1 eq
n 1 eq/mol 1 eq/mol
EM FM/1 FM/1
 EM in Precipitation and Complex Formation
➢ The EM of a participant in a precipitation or a complex formation reaction is that
mass which reacts with or provides one mole of the reacting cation if it is univalent,
one-half mole if it is divalent, one-third mole if it is trivalent, etc.
➢ Therefore the valency of the metal cation (ion charge) determines the number of
equivalents; # of eq anion = # eq cation

Reaction 2 Ba(NO3)2 + Na2SO4 → BaSO4 (s) + 2 NaNO3

Ionic equation Ba2+ + SO42− → BaSO4 (s)
# mol 1 mol 1 mol
# eq 2 eq 2 eq
n 2 eq/mol 2 eq/mol
EM FM/2 FM/2
 EM in Precipitation and Complex Formation
➢ The EM of a participant in a precipitation or a complex formation reaction is that
mass which reacts with or provides one mole of the reacting cation if it is univalent,
one-half mole if it is divalent, one-third mole if it is trivalent, etc.
➢ Therefore the valency of the metal cation (ion charge) determines the number of
equivalents; # of eq anion = # eq cation

Reaction 3 AgNO3 + 2 NaCN → Na[Ag(CN)2] + NaNO3

Ionic equation Ag+ + 2 CN− → Ag(CN)2−
# mol 1 mol 2 mol
# eq 1 eq 1 eq
n 1 eq/mol 1 eq/2 mol
EM FM/1 FM/(1/2) or 2 FM
 EM in terms of FM/n
SAQ 2.3 (16 pts) Balance the reactions or half-reactions in redox reaction and
determine the EM of the following substances
Unbalanced Equation Substance EM
CaO FM/2
e.g. CaO + HCl → CaCl2 + H2O
HCl FM/1

1 Cr2O72- + C2O42- + H+ → Cr3+ + CO2 + H2O

2 CaCl2 + K2SO4 → CaSO4(s) + KCl

3 Zn2+ + OH− → Zn(OH)42−

4 Na2CO3 + HNO3 → H2CO3 + NaNO3

 EM in terms of FM/n
e.g.
 Mole Approach vs. Equivalent Approach
For a general reaction: aA + bB → cC +dD

Mole Approach Equivalent Approach

𝒂
# 𝒎𝒐𝒍 𝑨 = # 𝒎𝒐𝒍 𝑩 × # 𝒆𝒒 𝑨 = # 𝒆𝒒 𝑩
𝒃
𝒂 𝑵𝑨 𝑽𝑨 = 𝑵𝑩 𝑽𝑩
𝑴 𝑨 𝑽𝑨 = 𝑴 𝑩 𝑽𝑩 ×
𝒃
 Molarity and Normality
Relationship between Molarity and Normality
N = nM and M = N/n

SAQ 2.4 (4 pts) A solution containing 25.0 mL of oxalic acid required 13.78
mL of 0.04162 N KMnO4 for titration forming Mn2+ and CO2 as products.
Calculate the normality and molarity of the oxalic acid.
 Normality and Titer
SAQ 2.5 (3 pts) Calculate the normality of a HCl (36.461) solution having a sodium
carbonate titer of 5.00 mg/mL.
FM: HCl = 36.461, Na2CO3 = 106.0
 T = 5.00 mg Na2CO3 / mL HCl
 Dilution
A dilute solution can be prepared by taking an aliquot (or portion) from a more
concentrated solution
➢ moles from concentrated solution = moles placed in dilute solution
➢ Mole Approach: Mconc x Vconc = Mdil x Vdil
➢ Equivalent Approach: Nconc x Vconc = Ndil x Vdil

SAQ 2.6 (3 pts) You wish to prepare 500. mL of 0.100 M K2Cr2O7 solution from a 0.250
M solution. Assuming that volumes are additive, what volume of the 0.250 M solution
must be diluted to 500. mL?
 Dilution and Aliquot
Example 2-3
A 10.0 mL aliquot of H2SO4 solution was diluted to 100.0 mL. Then 25.0 mL aliquot of
the diluted H2SO4 solution was titrated with 30.0 mL of 0.200 M NaOH solution using
phenolphthalein as indicator. What is the molar concentration of the original H2SO4
solution?

Reaction: H2SO4 + 2NaOH → Na2SO4 + 2H2O

Ionic Equilibria Calculations
 Learning Outcomes
➢ Distinguish the different chemical equilibria and equilibrium expressions
➢ Explain the effects of various factors on equilibrium states
➢ Explain the significance of thermodynamic equilibrium constants
➢ Explain the concept of mass balance and charge balance equations
➢ Solve problems involving multiple equilibria
 Chemical Equilibrium
➢ dynamic state : ratef= rateb
➢ Equilibrium State: the ratio of concentrations of reactants and products
is constant
➢ Le Châtelier’sprinciple: the position of an equilibrium always shifts in
such a direction as to relieve a stress that is applied to the system
➢ Mass-action Effect: an equilibrium shift brought about by changing the
amount of one or more participating species.
 Types of Equilibria and Equilibrium Constants

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 204

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 205
 Activity Effect or Salt Effect on Equilibrium
➢ Generally, the presence of diverse salts (not containing ions common to the
equilibrium involved) will shift equilibrium towards formation of more ions.
➢ The electrostatic attraction between the ions of the electrolyte and the ions of
opposite charge from the reacting species decreases the effective concentration of
the ions of the equilibrium reaction thereby shifting the equilibrium.
e.g. Kw = 1.0 x 10−14 (in 10−6 M NaCl)
Kw’ = 1.7 x 10−14 (in 10−1 M NaCl)
Consider this equilibrium: 𝐻2 𝑂 ⇄ 𝐻 + + 𝑂𝐻 −
How will the presence of Na+ and Cl− affect the equilibrium?

Na+ will be attracted to OH− and Cl− will be attracted to H+

 Equilibrium shifts towards formation of more H+ and OH− and therefore the ion
product of H2O increases to a new value Kw’
 Effect of electrolyte
concentration on
concentration-based
equilibrium constants K’

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 236

Equilibrium Constants: Thermodynamic (K) and Concentration-Based (K’)

For the reaction: aA + bB ⇄ cC + dD

since a = C

Since  is difficult to calculate

𝛾𝐶𝑐 𝛾𝐷𝑑 [𝐶]𝐶 [𝐷]𝑑 𝛾𝐶𝑐 𝛾𝐷𝑑 due to some unknown
𝐾= 𝑎 𝑏 𝑎 𝑏
= 𝑎 𝑏 𝐾′ parameters, most calculations
𝛾𝐴 𝛾𝐵 [𝐴] [𝐵] 𝛾𝐴 𝛾𝐵 use K’ instead of K.
Activity and Activity is the effective concentration of an ion in the presence
of electrolytes:
Ionic Strength
ai = iCi where ai = activity of ion i
i = activity coefficient of ion i
Activity Ci = molarity of ion i

Ionic strength () is a property of a solution that depends on

the total concentration of ions in the solution as well as on the
charge carried by each of these ions.

where Zi = charge of ion i

In very dilute solutions:  → 0 i →1 ai → Ci

 Effect of electrolyte
concentration on the
solubility of some salts
for compounds
containing ions of
different charge

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 237

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 238
The Effect of Ionic Strength

The effect of added electrolyte on equilibria is independent of the

chemical nature of the electrolyte but depends on a property of the
solution called the ionic strength, which is defined as

where [A], [B], [C], . . . represent the species molar concentrations of

ions A, B, C, . . . and ZA, ZB, ZC, . . . are their charges.
 Example 2-4

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 238

 Ionic Strength

SAQ 2.7 Calculate the ionic strength of a solution that is 0.010 M in La(NO3)3 and 0.020
M in Fe(NO3)2.
 Activity Coefficient

for aqueous solns at 25oC

where

i = activity coefficient of the species i

Zi = charge on the species i
μ = ionic strength of the solution
α = effective diameter of the hydrated ion i
Debye – Hückel Equation
in nm (10-9 m)
 IO4−

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 242

 Properties of
Activity Coefficients
1. As → 0, X → 1, aX → [X],
and Ksp→ Ksp

2. In solutions that are not too

concentrated, the activity
coefficient for a given species is
independent of the nature of the
electrolyte and dependent only on
the ionic strength.

3. For a given ionic strength, the

activity coefficient of an ion
decreases more dramatically from
unity as the charge on the species
Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 240 increases.
➢Hydrated ions: Properties of
positive ions bind
through the oxygen
Activity Coefficients
atoms, negative 4) The activity coefficient of an
ions through the uncharged molecule is
hydrogen atoms approximately unity, no matter
what the level of ionic strength.
➢Ionic and hydrated
radii of several ions 5) At any given ionic strength,
➢Smaller, more the activity coefficients of ions of
highly charged ions the same charge are
bind water approximately equal; the small
molecules more variations among ions of the
tightly and behave same charge can be correlated
as larger hydrated with the effective diameter of the
species hydrated ions (); the smaller ,
the more important activity
effects become (activity
Harris, Quantitative Chemical Analysis, 9th ed, p 161 coefficient << unity)
Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, 240
 Activity coefficient
Example 2-5
Calculate the activity coefficient for Hg2+ in a solution that has an ionic strength of
0.085 M. Use 0.5 nm for the effective diameter of the ion.

2
0.51 × +2 × 0.085
−𝑙𝑜𝑔 𝛾𝐻𝑔2+ =
1 + 3.3 × 0.5 𝑛𝑚 × 0.085

𝛾𝐻𝑔2+ = 0.397 = 0.4

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 243

 Activity coefficient
SAQ 2.8 (3 pts)
Find the activity coefficient of Ca2+ in a solution of 3.3 mM CaCl2. (Ca has a size of 600
pm; 1 nm = 1000 pm)
Thermodynamic (K) and Concentration-Based (K’)
SAQ 2.9 (3 pts)
Given the following:
Ksp of La(IO3)3 is 1.0 × 10−11
At  = 0.050, : La3+ = 0.24, IO3− = 0.82​
calculate the Ksp' of La(IO3)3 at  = 0.050.

La(IO3)3 ⇄ La3+ + 3 IO3−

Example 2-6

Error introduced
when molar
concentrations
are used to
approximate
activities

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 244-245

Error introduced
when molar
concentrations
are used to
approximate
activities

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 244-245

Error introduced
when molar
concentrations
are used to
approximate
activities

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 244-245

Error introduced when molar concentrations are used to approximate activities
SAQ 2.10 (12 pts)
Calculate the solubility of PbI2 (Ksp = 7.9 × 10−9) in a 0.0333 M solution of Mg(ClO4)2 using
(a) activities and (b) molar concentrations.
 (nm): Pb2+ = 0.45, I− = 0.30
PbI2 ⇄ Pb2+ + 2 I− Let s = [Pb2+] 2s = [I−]

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 247

Solving Multiple-
Equilibrium constant
Equilibrium Problems expressions
Using a Systematic
Method

From balanced charge balance equation

chemical equations,
write as many
independent equations
as there are chemical
species in the system mass balance equation
being studied
 Mass-Balance Equations (MBEs)

relate the equilibrium derived from information

concentrations of various about how the solution
species in a solution to was prepared and from
one another and to the knowledge of the kinds
analytical concentrations of equilibria established
of the various solutes in the solution
Example 2-7
Write the equation of mass balance for a 0.100 M solution of acetic acid.

The equilibria are:

HOAc ⇄ H+ + OAc-
H2O ⇄ H+ + HO-

Equilibrium concentration of acetic acid, CHOAc = sum of the equilibrium

concentrations of all its species

CHOAc = [HOAc] + [OAc-]

CHOAc = 0.100 M

Equilibrium concentration of H+, CH = [OAc-] + [HO-]

 [+] = [−]
Charge-Balance
Equation (CBE) • [+] = concentration of positive
species x magnitude of charge
• [−] = concentration of negative
species x magnitude of charge
principle of the coefficient in front of each
electroneutrality in a species always equals the magnitude
reaction of the charge on the ion
• If : [PO43-] = 0.01, then the negative
charge in
• 3[PO43-] = 3(0.01) = 0.03 M
 CBE
Suppose a solution contains ionic species at the following concentrations:
[H+] = 5.1 x 10-12 M [H2PO4-] = 1.3 x 10-6 M
[K+] = 0.0550 M [HPO42-] = 0.0220 M
[OH-] =0.0020 M [PO43-] = 0.0030 M

The charge balance is:

[H+] +[K+] = [OH-] + [H2PO4-] + 2[HPO42-] + 3[PO43-]

Are the charges balanced ?

Considering the positive charges :

(5.1 x 10-12) + 0.0550 = 0.0550

Considering the negative charges :

0.0020 + (1.3 x 10-6) + 2(0.0220) + 3(0.0030) = 0.0550
 MBEs and CBE
Example 2-8
For a 0.010 M NH3 solution that is saturated with AgBr
+ –
Pertinent equilibria: AgBr(solid) ⇄ Ag (aq) + Br (aq)
+ +
Ag (aq) + NH3 (aq) ⇄ Ag(NH3) (aq)
+ +
Ag(NH3) + NH3 ⇄ Ag(NH3)2
NH3 + H2O ⇄ NH4+ + OH–
2H2O ⇄ H3O+ + OH–
+ + + –
MBEs: [Ag ] + [Ag(NH3) ] + [Ag(NH3)2 ] = [Br ]
+ +
cNH3 = [NH3] + [NH4+] + [Ag(NH3) ] +2[Ag(NH3)2 ] = 0.010
[OH–] = [NH4+] + [H3O+]
+ + + –
CBE: [Ag ] + [Ag(NH3) ] + [Ag(NH3)2 ] + [NH4+] + [H3O+] = [OH–] + [Br ]
Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 252-253
 MBEs and CBE
SAQ 2.11 (6 pts)
Write MBE and CBE for a 0.100 M H3PO4

Pertinent Equilibria:
H3PO4 + H2O ⇄ H3O+ + H2PO4− Ka1
H2PO4− + H2O ⇄ H3O+ + HPO42− Ka2
HPO42− + H2O ⇄ H3O+ + PO43− Ka3
2H2O ⇄ H3O+ + OH− Kw

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 277

 MBEs and CBE
SAQ 2.12 (6 pts)
Write MBE and CBE for a 0.200 M Na2HPO4

Pertinent Equilibria:
H3PO4 + H2O ⇄ H3O+ + H2PO4− Ka1
H2PO4− + H2O ⇄ H3O+ + HPO42− Ka2
HPO42− + H2O ⇄ H3O+ + PO43− Ka3
2H2O ⇄ H3O+ + OH− Kw

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 277

 MBEs and CBE
Example 2-9 (Common ion effect)
Write MBE and CBE for a 0.12 M NaF and saturated with CaF2

Pertinent Equilibria:
CaF2(s) ⇄ Ca2+ + 2 F− Ksp
F− + H3O+ ⇄ HF + 2H2O 1/Ka
2H2O ⇄ H3O+ + OH− Kw
Let Cca = [Ca2+] = s and CF = CNaF + 2s

MBEs: CF = [HF] + [F−] = 0.12 + 2[Ca2+]

[Na+] = 0.12 mol/L

CBE: 2[Ca2+] + [Na+] + [H3O+] = [F−] + [OH−]

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, p 277
Systematic
method for
solving
multiple
equilibrium
problems

Steps 3, 4, and 5
may be
interchanged
 Example 2-10

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 257-258

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 257-258
Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 257-258
 Example 2-11

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 258-259

Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 258-259
Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 258-259
Skoog, et al. Fundamentals of Analytical Chemistry, 9th ed, pp 258-259
Systematic method for solving multiple equilibrium problem
Dependence of Solubility on pH
Example 2-12
Find the solubility of CaF2 in water at pH = 3.00, given:
[HF][OH-]
Ksp = [Ca2+][F-]2 = 3.9 x 10-11 and Kb = = 1.5 x 10-11
[F-]

Step 1: write the balanced chemical equations

CaF2(s) ⇄ Ca2+ + 2F-
F- + H2O ⇄ HF + OH-
H2O ⇄ H+ + HO-

Step 2: Define unknown: let s = [Ca2+]

Step 3: Write equilibrium constant expressions
Ksp = [Ca2+][F-]2 = 3.9 x 10-11 (1)
[HF][OH-]
Kb = = 1.5 x 10-11 (2)
[F-]
Kw = [H+] [HO-] = 1.0 x 10-14 (3)

Step 4: Write the MBEs

CF =[F-] + [HF] = 2[Ca2+] (4)

Step 5: Write CBE
[H+] + 2[Ca2+] = [F-] + [HO-] (5)

Step 6: Count the number of equations and unknowns

There are five equations and five unknowns ([Ca2+], [F⁻], [OH⁻], [H+] and [HF])
Step 7: make suitable approximations to simplify the mathematics

Let the pH of the solution be 3.00

[H+] = 1.0 x 10-3 M

From (3) [HO-] = 1.0 x 10-14/ 1.0 x 10-3

= 1.0 x 10-11
[HF] Kb 1.5 x 10-11
From (2) = = 1.0 x 10-11
[F-] [HO-]
= 1.5

[HF] = 1.5[F-] (6)

From (4) [F-] + [HF] = 2[Ca2+]

[F-] + 1.5[F-] = 2[Ca2+]

[F-] = 0.80[Ca2+] (7)

 From (1) Ksp = [Ca2+][F-]2 = 3.9 x 10-11

[Ca2+](0.80 [Ca2+])2 = 3.9 x 10-11

[Ca2+] = 3.9 x 10-4 M = s

Concentrations of other species:

From (7) [F-] = 0.80[Ca2+]

= 3.1 x 10-4 M

From (6) [HF] = 1.5[F-]

= 4.7 x 10-4 M
SAQ 2.13 (12 pts) Supply Steps 4-9 in the calculation of the molar solubility, s, of
Mn(OH)2 in water. Ksp= 2 x 10-13
Step 1: Write the balanced chemical equations

Mn(OH)2 ⇄ Mn2+ + 2OH⁻

2H2O ⇄ H3O+ + OH⁻

Step 2: Define unknown

Let s = [Mn2+]

Step 3: Write equilibrium constant expressions

Ksp= [Mn2+][OH⁻]2= 2 x 10⁻13
Kw = [H3O+][OH⁻] = 1.0 x 10⁻14
Step 4: Write MBEs

Step 5: Write CBE

Step 6: Count the number of equations and unknowns

Step 7: Make suitable approximations

Step 8: Solve for unknown

Step 9: Check validity of assumption