Week 1 - Chapter 4 Calculations Used in Analytical Chemistry

CALCULATIONS USED
IN ANALYTICAL
CHEMISTRY
Chapter 4
A. SOME IMPORTANT UNITS OF
MEASUREMENT
MEASUREMENT
A-1 SI Units
 Scientists throughout the world have adopted a

standardized system of units known as the
International System of Units (SI).
 This system is based on the seven fundamental

base units.
SI Base Units
SI Base Units
MEASUREMENT
A-2 The Distinction Between Mass and Weight
 Mass is an invariant measure of the quantity of

matter in an object.
 Weight is the force of attraction between an

object and its surroundings, principally the earth.
 Because gravitational attraction varies with
geographical location, the weight of an object
depends on where you weigh it.
MEASUREMENT
A-2 The Distinction Between Mass and Weight
 Weight and mass are related by the familiar

expression
w = mg
 where w is the weight of an object, m is its mass,

and g is the acceleration due to gravity.
MEASUREMENT
A-3 The Mole
 The mole (abbreviated mol) is the SI unit for the amount of
a chemical substance.
 It is always associated with specific microscopic entities
such as atoms, molecules, ions, electrons, other particles,
or specified groups of such particles as represented by a
chemical formula.
 It is the amount of the specified substance that contains
the same number of particles as the number of carbon
atoms in exactly 12 grams of 12C. This important number is
Avogadro’s number
NA = 6.022 x 1023
MEASUREMENT
A-3 The Mole
 The molar mass M of a substance is the mass in grams of

1 mole of that substance.
 We calculate molar masses by summing the atomic
masses of all the atoms appearing in a chemical formula.
 For example, the molar mass of formaldehyde CH2O is
MEASUREMENT
A-4 The Millimole
 The millimole is 1/1000 of a mole, and the mass in

grams of a millimole, the millimolar mass (mM), is
likewise 1/1000 of the molar mass.
 1 mmol = 10-3 mol, and 103 mmol = 1 mol

MEASUREMENT
A-5 Calculating the Amount of a Substance in
Moles or Millimoles
Example 1
Find the number of moles and millimoles of benzoic
acid (M = 122.1 g/mol) that are contained in 2.00 g
of the pure acid.
MEASUREMENT
A-5 Calculating the Amount of a Substance in
Moles or Millimoles
Example 2
What is the mass in grams of Na+ (22.99 g/mol) in
25.0 g of Na2SO4 (142.0 g/mol)?
MEASUREMENT
Practice:
1. Find the amount of the indicated element (in
moles) in
(a) 8.75 g of B2O3
2. Find the amount in millimoles of the indicated
species in
(a) 850 mg of P2O5
3. Find the number of Na+ ions in 2.92 g of NaOH (40
g/mol)?
B. SOLUTIONS AND THEIR
CONCENTRATIONS
CONCENTRATIONS
B-1 Concentration of Solutions
Four fundamental ways of expressing solution

concentration:
1. molar concentration
2. percent concentration
3. solution-diluent volume ratio, and
4. p-functions
CONCENTRATIONS
Molar Concentration
 The molar concentration cx of a solution of a solute
species X is the number of moles of that species that is
contained in 1 liter of the solution (not 1 L of the
solvent).
 In terms of the number of moles of solute, nx, and the
volume, V, of solution, we write
CONCENTRATIONS
Molar Concentration
 The unit of molar concentration is molar,

symbolized by M, which has the dimensions of
mol/L, or mol L-1.
 Molar concentration is also the number of

millimoles of solute per milliliter of solution.
CONCENTRATIONS
Example
Calculate the molar concentration of ethanol in an
aqueous solution that contains 2.30 g of C2H5OH
(46.07 g/mol) in 3.50 L of solution.
CONCENTRATIONS
Molar Analytical Concentration
 is the total number of moles of a solute, regardless

of its chemical state, in 1 L of solution.
 The molar analytical concentration describes how

a solution of a given concentration can be
prepared.
CONCENTRATIONS
Molar Equilibrium Concentration
 refers to the molar concentration of a particular

species in a solution at equilibrium.
 To specify the molar equilibrium concentration of

a species, it is necessary to know how the solute
behaves when it is dissolved in a solvent.
CONCENTRATIONS
Molar Equilibrium Concentration
 For example, the molar equilibrium concentration of

H2SO4 in a solution with a molar analytical
concentration cH2SO4 = 1.0 M is actually 0.0 M
because the sulfuric acid is completely dissociated
into a mixture of H+, HSO4-, SO4- ions. There are
essentially no H2SO4 molecules in this solution.
 The equilibrium concentrations of the ions are 1.01,

0.99, and 0.01M, respectively.
CONCENTRATIONS
Example 4
Calculate the analytical and equilibrium molar
concentrations of the solute species in an aqueous
solution that contains 285 mg of trichloroacetic
acid, Cl3CCOOH (163.4 g/mol), in 10.0 mL (the
acid is 73% ionized in water).
CONCENTRATIONS
Example 5
Describe the preparation of 2.00 L of 0.108 M BaCl2
from BaCl2 · 2H2O (244.3 g/mol).
CONCENTRATIONS
Example 6
Describe the preparation of 500 mL of 0.0740 M Cl2
solution from solid BaCl2 · 2H2O (244.3 g/mol).
CONCENTRATIONS
Percent Concentration
 Three common methods:

CONCENTRATIONS
 Weight percent is often used to express the

concentration of commercial aqueous reagents.
 For example, nitric acid is sold as a 70% (w/w)
solution, meaning that the reagent contains 70 g
of HNO3 per 100 g of solution.
CONCENTRATIONS
 Volume percent is commonly used to specify the
concentration of a solution prepared by diluting a
pure liquid compound with another liquid.
 For example, a 5% (v/v) aqueous solution of
methanol usually describes a solution prepared by
diluting 5.0 mL of pure methanol with enough
water to give 100 mL.
CONCENTRATIONS
 Weight or volume percent is often used to indicate
the composition of dilute aqueous solutions of
solid reagents.
 For example, 5% (w/v) aqueous silver nitrate often
refers to a solution prepared by dissolving 5 g of
silver nitrate in sufficient water to give 100 mL of
solution.
CONCENTRATIONS
Parts per Million and Parts per Billion
 For very dilute solutions, parts per million (ppm) is

a convenient way to express concentration:
where cppm is the concentration in parts per

million.
CONCENTRATIONS
Parts per Million and Parts per Billion
 A handy rule in calculating parts per million is to

remember that for dilute aqueous solutions whose
densities are approximately 1.00 g/mL, 1 ppm =
1.00 mg/L. That is,
CONCENTRATIONS
Example 7
What is the molar concentration of K+ in a solution
that contains 63.3 ppm of K3Fe(CN)6 (329.3
g/mol)?
CONCENTRATIONS
Solution-Diluent Volume Ratios
 The composition of a dilute solution is sometimes
specified in terms of the volume of a more
concentrated solution and the volume of solvent used
in diluting it.
 The volume of the former is separated from that of
the latter by a colon. Thus, a 1:4 HCl solution contains
four volumes of water for each volume of
concentrated hydrochloric acid.
CONCENTRATIONS
p-Functions
 Scientists frequently express the concentration of a
species in terms of its p-function, or p-value.
 The p-value is the negative logarithm (to the base 10) of
the molar concentration of that species. Thus, for the
species X,
pX = -log [X]
 p-values offer the advantage of allowing concentrations
that vary over ten or more orders of magnitude to be
expressed in terms of small positive numbers.
CONCENTRATIONS
Example 8
Calculate the p-value for each ion in a solution that is
2.00 x 10-3 M in NaCl and 5.4 x 10-4 M in HCl.
CONCENTRATIONS
B-2 Density and Specific Gravity of Solutions
 The density of a substance is its mass per unit

volume, and its specific gravity is the ratio of its
mass to the mass of an equal volume of water at
4°C.
 Density has units of kilograms per liter or grams
per milliliter in the metric system. Specific gravity
is dimensionless and so is not tied to any particular
system of units.
CONCENTRATIONS
Example 10
Calculate the molar concentration of HNO3 (63.0
g/mol) in a solution that has a specific gravity of
1.42 and is 70.5% HNO3 (w/w).
CONCENTRATIONS
Example 11
Describe the preparation of 100 mL of 6.0 M HCl
from a concentrated solution that has a specific
gravity of 1.18 and is 37% (w/w) HCl (36.5 g/mol).
CONCENTRATIONS
Example 11
Describe the preparation of 100 mL of 6.0 M HCl
from a concentrated solution that has a specific
gravity of 1.18 and is 37% (w/w) HCl (36.5 g/mol).
CONCENTRATIONS
Practice:
1. Find the number of millimoles of solute in
(a) 2.00 L of 0.0555 M KMnO4.
(b) 3.50 L of a solution that contains 3.33 ppm of
CuSO4.
2. Calculate the p-value for each of the indicated
ions:
Na+, Cl-, and OH- in a solution that is 0.0635 M
in NaCl and 0.0403 M in NaOH.
CONCENTRATIONS
Practice:
3. A 6.42% (w/w) Fe(NO3)3 (241.86 g/mol) solution

has a density of 1.059 g/mL. Calculate
(a) the molar analytical concentration of Fe(NO3)3
in this solution.
(b) the molar NO3- concentration in the solution.
(c) the mass in grams of Fe(NO3)3 contained in
each liter of this solution.
CONCENTRATIONS
Practice:
4. Describe the preparation of 750 mL of 6.00 M

H3PO4 from the commercial reagent that is
86% H3PO4 (w/w) and has a specific gravity of
1.71.
C. CHEMICAL STOICHIOMETRY
Stoichiometry is the quantitative relationship

among the amounts of reacting chemical species.
 The stoichiometry of a reaction is the relationship

among the number of moles of reactants and
products as represented by a balanced chemical
equation.
C-1 Empirical Formulas and Molecular Formulas
 An empirical formula gives the simplest whole

number ratio of atoms in a chemical compound.
 In contrast, a molecular formula specifies the

number of atoms in a molecule.
 Two or more substances may have the same

empirical formula but different molecular
formulas.
 For example, CH2O is both the empirical and the

molecular formula for formaldehyde; it is also the
empirical formula for such diverse substances as
acetic acid, C2H4O2; glyceraldehyde, C3H6O3; and
glucose, C6H12O6, as well as more than 50 other
substances containing 6 or fewer carbon atoms.
 A structural formula provides additional

information.
 For example, the chemically different ethanol and
dimethyl ether share the same molecular formula
C2H6O.
 Their structural formulas, C2H5OH and CH3OCH3,
reveal structural differences between these
compounds that are not shown in their common
molecular formula.
 Flow diagram for making stoichiometric calculations. (1) When the

mass of a reactant or product is given, the mass is first converted to
the number of moles, using the molar mass. (2) The stoichiometric
ratio given by the chemical equation for the reaction is then used to
find the number of moles of another reactant that combines with
the original substance or the number of moles of product that forms.
(3) Finally, the mass of the other reactant or the product is computed
from its molar mass.
C-2 Stoichiometric Calculations
 A balanced chemical equation gives the combining
ratios, or stoichiometry—in units of moles—of reacting
substances and their products.
 Therefore, the equation
2NaI(aq) + Pb(NO3)2(aq) → PbI2(s) + 2NaNO3(aq)
indicates that 2 moles of aqueous sodium iodide
combine with 1 mole of aqueous lead nitrate to
produce 1 mole of solid lead iodide and 2 moles of
aqueous sodium nitrate.
Example 12
(a) What mass of AgNO3 (169.9 g/mol) is needed to
convert 2.33 g of Na2CO3 (106.0 g/mol) to
Ag2CO3?
(b) What mass of Ag2CO3 (275.7 g/mol) will be
formed?
Example 13
What mass of Ag2CO3 (275.7 g/mol) is formed when
25.0 mL of 0.200 M AgNO3 are mixed with 50.0 mL
of 0.0800 M Na2CO3?
Example 14
What will be the molar analytical concentration of
Na2CO3 in the solution produced when 25.0 mL of
0.200 M AgNO3 is mixed with 50.0 mL of 0.0800 M
Na2CO3?
Practice:
1. Exactly 0.2220 g of pure Na2CO3 was dissolved

in 100.0 mL of 0.0731 M HCl.
(a) What mass in grams of CO2 were evolved?
(b) What was the molar concentration of the
excess reactant (HCl or Na2CO3)?
Practice:
2. Exactly 75.00 mL of a 0.3132 M solution of Na2SO3

were treated with 150.0 mL of 0.4025 M HClO4
and boiled to remove the SO2 formed.
(a) What was the mass in grams of SO2 that was
evolved?
(b) What was the concentration of the unreacted
reagent (Na2SO3 or HClO4) after the reaction
was complete?

Week 1 - Chapter 4 Calculations Used in Analytical Chemistry

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CALCULATIONS USED

 Scientists throughout the world have adopted a

 This system is based on the seven fundamental

 Mass is an invariant measure of the quantity of

 Weight is the force of attraction between an

 Weight and mass are related by the familiar

 where w is the weight of an object, m is its mass,

 The molar mass M of a substance is the mass in grams of

 The millimole is 1/1000 of a mole, and the mass in

 1 mmol = 10-3 mol, and 103 mmol = 1 mol

Four fundamental ways of expressing solution

 The unit of molar concentration is molar,

 Molar concentration is also the number of

Molar Analytical Concentration

 is the total number of moles of a solute, regardless

 The molar analytical concentration describes how

Molar Equilibrium Concentration

 refers to the molar concentration of a particular

 To specify the molar equilibrium concentration of

 For example, the molar equilibrium concentration of

 The equilibrium concentrations of the ions are 1.01,

 Three common methods:

 Weight percent is often used to express the

Parts per Million and Parts per Billion

 For very dilute solutions, parts per million (ppm) is

where cppm is the concentration in parts per

Parts per Million and Parts per Billion

 A handy rule in calculating parts per million is to

 The density of a substance is its mass per unit

3. A 6.42% (w/w) Fe(NO3)3 (241.86 g/mol) solution

4. Describe the preparation of 750 mL of 6.00 M

Stoichiometry is the quantitative relationship

 The stoichiometry of a reaction is the relationship

 An empirical formula gives the simplest whole

 In contrast, a molecular formula specifies the

 Two or more substances may have the same

 For example, CH2O is both the empirical and the

 A structural formula provides additional

 Flow diagram for making stoichiometric calculations. (1) When the

1. Exactly 0.2220 g of pure Na2CO3 was dissolved

2. Exactly 75.00 mL of a 0.3132 M solution of Na2SO3

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