Calculations Used

in Analytical
Chemistry
 Chapter Objectives (1 of 3)
By the end of this chapter, you should know:
• The International Systems of Units (SI) is based on seven
fundamental base units—kilogram, meter, mole, ampere, second, kelvin,
and candela.
• Revisions were made in 2019 to redefine the kilogram, the ampere, the
mole, and the kelvin.
• There is a difference between mass and weight. Mass is a measure of
the amount of matter in a substance, while weight is the force of
attraction between an object and its surroundings.
 Chapter Objectives (2 of 3)
• One mole of any entity (atoms, electrons, ions, or molecules) contains
Avogadro’s number of these entities.
• Avogadro’s constant is an exact number
Avogadro’s number is Avogadro’s constant per mole.

• The molar mass of a substance is the number of grams of that substance in 1

mole of that substance.

• Solution concentrations can be expressed as molar concentrations, parts

per million or billion, p-functions, or percentages.
 Chapter Objectives (3 of 3)
• Molar concentrations can be molar analytical or molar
equilibrium concentrations.

• Microsoft Excel can calculate concentrations and stoichiometric

quantities in chemical reactions.
Important Equations

Concentration in parts per million

p-Functions
pX = –log[X]
Dilution equation
 2A-1 SI Units (1 of 2)
• 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 shown in Table 2-1 (SI Base Units).

SI Base Units

Physical Quantity Name of Unit Abbreviation

Mass kilogram kg
Length meter m
Time second s
Temperature kelvin K
Amount of substance mole mol
Electric current ampere A
Luminous intensity candela cd
 2A-1 SI Units (2 of 2)

To express small or large measured

quantities in terms of a few simple digits,
prefixes are used with these base units and
other derived units. As shown in Table 2-2,
these prefixes multiply the unit by various
powers of 10.
 2A-2 The Distinction Between Mass and
Weight
• Mass is an unchanging measure of the quantity of matter in an object.
Weight is the force of attraction between an object and its surroundings,
principally Earth. Because gravitational attraction varies with
geographical location, the weight of an object depends on where you
weigh it.
• Weight and mass are related by the familiar expression below.
w = mg
• In this expression, w is the weight of an object, m is its mass, and g is
the acceleration due to gravity.
 2A-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. One mole contains exactly
elementary entities (atoms, molecules, ions, electrons, and so on).
• The fixed number is known as Avogadro’s constant.
• When expressed in the unit mol−1, this number is called Avogadro’s number,
which is often rounded to
• The molar mass M of a substance is the mass in grams of 1 mole of that
substance.
 2A-4 The Millimole

• Sometimes it is more convenient to make calculations with millimoles

(mmol) rather than moles.
• The millimole is 1/1000 of a mole.
• The millimolar mass (mM) is 1/1000 of the molar mass.
 Example 2-1
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.
Solution
If we use HBz to represent benzoic acid, we can write that 1 mole of HBz has a mass of
122.1 g. Therefore,

(2-1)

To obtain the number of millimoles, divide by the millimolar mass (0.1221 g/mmol), that is,
 Example 2-2 (2 of 2)
To obtain the mass of sodium in 25.0 g multiply the number of moles of
of by the molar mass of , or 22.99 g. And so,

Substituting the previous equation gives the mass in grams of

 Feature 2-2: The Factor-Label Approach to
Example 2-2 (1 of 2)
Some students and instructors find it easier to write out the solution to a problem
so that units in the denominator of each succeeding term eliminate the units in the
numerator of the preceding one until the units of the answer are obtained. This
method has been referred to as the factor-label method, dimensional analysis,
or the picket fence method. For instance, in Example 2-2, the units of the
answer are g and the units given are g Thus, we can write
 2B-1 Concentrations of Solutions (1 of 6)

• The molar concentration of a solution of a solute species X is the

number of moles of that species that is contained in 1 L of the solution (not
1 L of the solvent).
• Equation 2-2 describes the molar concentration in terms of the number of
moles of solute (n) and the volume (V) of solution,

(2-2)

▪ The unit of molar concentration is molar, symbolized by M, which has the

dimensions of
 Example 2-3
Calculate the molar concentration of ethanol in an aqueous solution that contains 2.30 g of
in 3.50 L of solution.
Solution
To calculate molar concentration, we must find both the amount of ethanol and the volume of the
solution. The volume is given as 3.50 L, so all we need to do is to convert the mass of ethanol to
the corresponding amount of ethanol in moles.

To obtain the molar divide the amount by the volume. Thus,

concentration,
 2B-1 Concentrations of Solutions (2 of 6)

• The molar analytical concentration, or analytical concentration, of a

solution gives the total number of moles of a solute in 1 L of the solution
(or the total number of millimoles in 1 mL).
 2B-1 Concentrations of Solutions (3 of 6)

• The molar equilibrium concentration, or just 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.
 Example 2-4 (1 of 2)
Calculate the analytical and equilibrium molar concentrations of the solute species in an aqueous
solution that contains 285 mg of trichloroacetic acid, (163.4 g/mol), in 10.0 mL (the
acid is 73% ionized in water).
Solution
As in Example 2-3, we calculate the number of moles of which we designate as HA,
and divide by the volume of the solution, 10.0 mL, or 0.0100 L. Therefore,

The molar analytical concentration, is then

 Example 2-4 (2 of 2)
In this solution, 73% of the HA dissociates, giving

The equilibrium concentration of HA is then 27% of Thus,

The equilibrium concentration of is equal to 73% of the analytical concentration of HA, that is,

Because 1 mole of is formed for each mole of we can also write

and
 2B-1 Concentrations of Solutions (4 of 6)
• Percent concentration can be expressed in several ways.
• Note that weight percent is commonly used but should more correctly be
called mass percent and is called mass concentration in IUPAC terminology.
 2B-1 Concentrations of Solutions (5 of 6)
• For very dilute solutions, parts per million (ppm) is a convenient way to
express concentration:

• The units of mass in the numerator and denominator must agree so

that they cancel.
• Parts per billion (ppb) and parts per thousand (ppt) are also used.
 2B-1 Concentrations of Solutions (6 of 6)

• Scientists frequently express the concentration of a species in

terms of its p-function (p-value).
• The p-value is the negative logarithm (to the base 10) of the molar
concentration of that species as shown below for the species X.
pX = −log [X]
 2B-2 Density and Specific Gravity of
Solutions (1 of 2)
• Density expresses the mass of a substance per unit volume.
▪ In SI units, density is expressed in units of kg/L or g/mL.
• Specific gravity is the ratio of the mass of a substance to the
mass of an equal volume of water.
 2B-2 Density and Specific Gravity of
Solutions (2 of 2)
• Equation 2-4 is helpful in preparing a diluted solution with the
volume and concentration given by the terms on the right.
• This equation can be used with L and mol/L or mL and mmol/mL
(the same units must be used for both solutions).

(2-4)
 2C 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.
 2C-1 Empirical Formulas and Molecular
Formulas
• An empirical formula gives the simplest whole number ratio of atoms in
a chemical compound.
• 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.

• A structural formula provides additional information by showing

structural differences between compounds.
▪ Two or more substances may have the same molecular formula but
different structural formulas.
 2C-2 Stoichiometric Calculations (1 of 2)

• A balanced equation gives the combining ratios or stoichiometry of

reacting substances and products.
• The physical state of substances appearing in equations is often
indicated by the letters (g), (l), (s), and (aq), which refer to gaseous,
liquid, solid, and aqueous solution states, respectively.
 2C-2 Stoichiometric Calculations (2 of 2)

• Figure 2-2 shows how to make stoichiometric calculations.

 Example 2-12 (1 of 2)

(a) What mass of (169.9 g/mol) is needed to convert 2.33 g of

(106.0 g/mol) to (b) What mass of 275.7 g/mol) is formed?
Solution
(a)
Step 1.
 Example 2-12 (2 of 2)
Step 2. The balanced equation reveals that

In this instance, the stoichiometric factor is

Step 3.
 Example 2-13 (1 of 2)
What mass of (275.7 g/mol) is formed when 25.0 mL of 0.200 M is mixed with 50.0 mL of 0.0800 M
Solution
Mixing these two solutions will result in one (and only one) of three possible outcomes:
(a) An excess of remains after the reaction is complete.
(b) An excess of remains after the reaction is complete.
(c) There is no excess of either reagent (that is, the number of moles of is exactly equal to twice the number of
moles of
As a first step, establish which of these situations applies by calculating the amounts of reactants (in moles) available
before the solutions are mixed.
The initial amounts are
 Example 2-13 (2 of 2)

Because each ion reacts with two ions,

is required to react with the
Since we have insufficient situation (b) prevails, and the number
of moles of produced will be limited by the amount of
available. Thus,
 Analytical Chemistry Online Activity

Search to find as many definitions of the kilogram as you can. Why

are there so many definitions? Describe the platinum-iridium
kilogram that was the standard prior to 2019. How is the 2019
definition an improvement on this prototype kilogram? Why is the
2019 definition a more stable value? Another proposed standard
prior to 2019 was the so-called silicon kilogram. Describe this
proposed standard, and compare it to the 2019 definition of the
kilogram.
 Key Terms Activity

• Density • Mole
• Excel calculations • Parts per million
• Mass • p-Function
• Molar analytical concentration • Specific gravity
• Molar concentration • Stoichiometry
• Molar equilibrium concentration • Weight
• Molar mass
 Challenge Problem (1 of 5)

2-41. Challenge Problem: Prior to the 2019 definition of Avogadro’s

number as an exact value, the number was calculated in various ways
from experimental measurements. According to Kenny et al.,
Avogadro’s number may be calculated from the following equation
using measurements on a sphere fabricated from an ultrapure single
crystal of silicon:
 Challenge Problem (2 of 5)

where
NA= Avogadro’s number
n = the number of atoms per unit cell in the crystal lattice of silicon = 8
MSi = the molar mass of silicon
V = the volume of the silicon sphere
m = the mass of the sphere
a = the crystal lattice parameter =
 Challenge Problem (3 of 5)

a) Derive the equation for Avogadro’s number.

b) From the recent data assembled by Andreas et al. on Sphere AVO28-S5 in
the following table, calculate the density of silicon and its uncertainty. You may
wish to delay the uncertainty calculations until you have studied Chapter 4.
 Challenge Problem (4 of 5)

c) Calculate Avogadro’s number and its uncertainty.

d) We have presented data for only one of the two silicon spheres used in these
studies. Look up the data for Sphere AVO28-S8 cited in note 3 and calculate a
second value for NA. After you have studied Chapter 5, compare your two
values for NA, and decide whether the difference in the two numbers is
statistically significant. If difference between the two values is not statistically
significant, calculate a mean value for Avogadro’s number determined from
the two spheres and the uncertainty of the mean.
 Challenge Problem (5 of 5)

e) Which of the variables in the table have the most significant influence on the
value that you calculated and why?
f) What experimental methods were used to make the measurements shown in
the table?
g) Comment on experimental variables that might contribute to the uncertainty in
each measurement.
h) Compare the 2019 exact value of Avogadro’s number with your computed
values. Discuss any differences and suggest possible causes for the
discrepancies.