CHE 401 : ANALYTICAL CHEMISTRY CHE 401 : ANALYTICAL CHEMISTRY

MODULE 2. CALCULATIONS USED IN ANALYTICAL CHEMISTRY Centi- c 10-2

Milli- m 10-3

2.1 UNITS OF MEASUREMENTS Micro- µ 10-6

Scientists throughout the world implemented a standardized system of units known as the Nano- n 10-9
International System of Units (SI). This system is based on the seven basic units depicted in
Pico- p 10-12
Table 2.1. From these base units are derived various other useful units, such as volts, hertz,
coulombs, and joules. Femto- f 10-15
Atto- a 10-18
Table 2.1 SI Base Units
Physical Quantity Name of Unit Abbreviation
Mass kilogram kg 2.2 DISTINCTION BETWEEN MASS AND WEIGHT

Length meter m Mass is an invariant measure of the amount of matter in an object.

Time second s
Weight is the force of attraction between an object and its surroundings, principally the earth.
Temperature kelvin K
Amount of Substance mole mol Gravitational attraction varies with geographical location, hence the weight of an object depends
on where you weigh it. Examples :
Electric Current ampere A
1. A crucible weighs less in Denver than in Atlantic City (both cities are at approximately
Luminous Intensity candela cd
the same latitude) because the attractive force between the crucible and the earth is
smaller at the higher altitude of Denver.
2. The crucible weighs more in Seattle than in Panama (both cities are at sea level), and
Prefixes are used with these base units and other derived units to express small or large measured the force of attraction increases measurably with latitude.
quantities in terms of a few simple digits. In analytical chemistry, we often determine the amount The mass of the crucible, however, remains constant regardless of where you measure it.
of chemical species by calculating masses. Metric units of kilograms (kg), grams (g), milligrams
(mg), or micrograms (µg) are used. Volumes of liquids are measured in units of liters (L), Relationship of mass and weight
milliliters (mL), and sometimes microliters (µL). Shown in Table 2.2, these prefixes multiply the Weight and mass are related by the familiar expression
unit by various powers of 10. W= mg (2.1)

Table 2.2 Prefixes for Units where W is the weight of an object, m is its mass, and g is the acceleration due to gravity.
Prefix Abbreviation Multiplier
A chemical analysis is always based on mass so that the results will not depend on locality. A
Giga- G 109 balance is used to compare the mass of an object with the mass of one or more standard masses.
Because g affects both unknown and known equally, the mass of the object is identical to the
Mega- M 106 standard masses with which it is compared.
Kilo- k 103
The distinction between mass and weight is often lost in common usage, and the process of
Deci- d 10-1 comparing masses is ordinarily called weighing. In addition, the objects of known mass as well as
the results of weighing are frequently called weights. Always bear in mind, however, that
CHE 401 : ANALYTICAL CHEMISTRY CHE 401 : ANALYTICAL CHEMISTRY

analytical data are based on mass rather than weight. Therefore, throughout this text we will use 2.4 METHODS OF EXPRESSING CONCENTRATIONS
mass rather than weight to: describe the amounts of substances or objects. On the other hand, for
lack of a better word, we will use "weigh" for the act of determining the mass of an object. Also, 2.4.1 Molar concentration
we will often say "weights" to mean the standard masses used in weighing. The molar concentration Cx of a solution of a chemical 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). The unit of molar
concentration is molarity, M, which has the dimensions of mol/L.
2.3 MOLE AND MILLIMOLE
Molarity also expresses the number of millimoles of a solute per milliliter of solution.

The Mole no. mole solute no.mmol solute

The SI unit used for the amount of a chemical species is called mole (abbreviated mol). It is always 𝐶𝑥 = = (2.2)
no. L solution no.mL solution
associated with a chemical formula and represents the number of particles represented by that
formulation by Avogadro (6.022 X 1023). A substance’s molar mass (MM) is the mass in grams of Example 2.3
1 mol of that substance. Molar masses are determined by summing the atomic masses of all the Obtain the molar concentration of ethanol
atoms appearing in a chemical formula.
1 mol C H OH
2.30g C2 H5 OH x 46.07g C2 H5 OH
Example 2.1 𝐶𝐶2𝐻5𝑂𝐻 = 2 5
The molar mass of formaldehyde, CH2O, is 3.50 L

1 mol C 12.0 g 2 mol H 1.0 g 1 mol O 16.0 g = 0.0143 mol C2H5OH / L = 0.0143 M
MWCH2O = mol CH x + x + x
2O mol C mol CH2 O mol H mol CH2 O mol O
Example 2.4
𝐠 Describe the preparation of 2.00 L of 0.108 M BaCl2 from BaCl2 • 2H2O (244.3 g/mol).
= 𝟑𝟎. 𝟎 𝐂𝐇 𝐎
𝐦𝐨𝐥 𝟐
To determine the number of grams of solute to be dissolved and diluted to 2.00 L, we note
Thus, 1 mol of formaldehyde has a mass of 30.0 g. that 1 mol of the dihydrate yields 1 mol of BaCl2. Therefore, to produce this solution we
will need
The Millimole
Often measurements of millimoles (mmol) are more convenient than moles, where millimole is 0.108 mol BaCl2 ∙ 2H2 O
1/100 of a mole. The mass in grams of a millimole of a substance is the millimolar mass which is 2.00 L x = 0.216mol BaCl2 ∙ 2H2 O
L
1/1000 of the molar mass.
The mass of BaCl2 • 2H2O is then
Example 2.2
Determine the number of moles and millimoles of benzoic acid (MM=122.1 g/mol) in 244.3g BaCl2 ∙ 2H2 O
2.00 g of the pure acid. If we use HBz to represent benzoic acid, we can write that 1 mol 0.216 mol BaCl2 ∙ 2H2 O x = 52.8g BaCl2 ∙ 2H2 O
mol BaCl2 ∙ 2 H2 O
of HBz has a mass of 122.1 g. Thus,

1 mol HBz
Amount of HBz = nHBz = 2.00 g HBz x 122.1 g HBz = 𝟎. 𝟎𝟏𝟔𝟒 𝐦𝐨𝐥 𝐇𝐁𝐳 *Dissolve 52.8 g of BaCl2 • 2H2O in water and dilute to 2.00 L.

To obtain the number of millimoles, we divide by the millimolar mass (0.1221 Example 2.5
mg/mmol). That is, Describe the preparation of 500 mL of 0.0740 M Cl - solution from solid BaCl2 • 2H2O
(244.3 g/mol).
1 mmol HBz
Amount of HBz = 2.00 g HBz 𝑥 = 16.4 mmol
0.1221 g HBz 0.0740 mol Cl− 1 mol BaCl2 ∙ 2H2 O
massBaCl2 ∙ 2H2 O = x 0.500L x
L 2 mol Cl−
CHE 401 : ANALYTICAL CHEMISTRY CHE 401 : ANALYTICAL CHEMISTRY

244.3g BaCl2 ∙ 2H2 O HA ⇌ H+ + A-

x = 4.52g BaCl2 ∙ 2H2 O
mol BaCl2 ∙ 2H2 O
The species molarity of HA is then 27% of cHA.

*Dissolve 4.52 g of BaCl2 • 2H2O in water and dilute to 0.500 L or 500mL. Thus,

[HA] = cHA x (100-73)/100 = 0.174 x 0.27 = 0.174 mol/L = 0.047 M

Analytical Molarity The species molarity of A- is equal to 73% of the analytical concentration of HA. That is,
The analytical molarity is the initial concentration of the solution. This is the concentration of the
solution right after the preparation in which there is no consumption of reactants nor creating 73 mol A− mol HA
products. [A] = 100 mol HA x 0.174 L
= 0.127 M

Equilibrium Molarity Because one mole H+ is formed for each mole of A-, we can also write
The equilibrium molarity describes the molar concentration of a given species in a solution at
equilibrium. To state the molarity of the species, it is important to know how the solute behaves
[H+] = [A-] = 0.127 M
when it is dissolved in a solvent. For example, the species molarity of H2SO4 in a solution with an
analytical concentration of 1.0 M is 0.0 M because the sulfuric acid is completely dissociated into
a mixture of H3O+, HSO4- and SO42- ions; essentially no H2SO4 molecules as such are present in 2.4.2 Molal concentration
this solution. The equilibrium concentrations and consequently the species molarity of these three
The molal concentration, Cx of the solution of a chemical species X is the number of moles of that
ions are 1.01, 0.99, and 0.01 M, respectively. Equilibrium molar concentrations are often
species that is contained in a kilogram of the solvent.
symbolized by putting square brackets around the chemical formula for the species, so we can
write an analytical concentration of 1.0 M for our solution of H2SO4 as
The unit of molar concentration is molality, m, which has the dimension of mol/kg. Molality also
express the number of millimoles of a solute per gram of the solvent.
[H2SO4] = 0.00 M [H3O+] = 1.01 M [HSO4-] = 0.99 M [SO42-] = 0.01 M
no of moles solute
𝑚 = kg solvent
(2.3)
Example 2.6
Calculate the analytical and equilibrium molar concentrations of the solute species in an Example 2.7
aqueous solution that contains 285 mg of trichloroacetic acid, Cl 3CCOOH (163.4 g/mol), Determine the molality of a solution containing 22.5grams NaOH dissolved in 2150 mL
in 10.0 mL trichloroacetic acid is 73% ionized in water. water at 4oC.
1 mole NaOH
Calculate the number of moles of Cl3CCOOH, which we will designate as HA, and divide 22.5 g NaOH [ ]
22.99 g Na+16g O+1.01g H
by the volume of the solution, 10.0 mL, or 0.01000 L. 𝑚= 1.0 g 1kg = 0.2616 𝑚
2150 mL H2O [ H2O][ ]
mL 1000 g

Thus,
1 g HA 1 mol HA
Amount HA = nHA = 285 mg HA x 1000 mg HA x 163.4 g HA
= 1.744 x 10−3 mol HA 2.4.3 Normal concentration

The normal concentration of the solution is the mass of the solute divided by the product of the
The molar analytical concentration, c HA, is then molecular weight and H+ equivalent per mole. This will be divided by the volume of the solution
in liter
1.744 x 10−3 mol HA 1000 mL mol HA
CHA = x = 0.174 = 0.174 M
10.0 mL 1L L Normal concentration is expressed in normality (N)
+ -
In this solution, 73% of the HA dissociates, giving H and A mass of the solute
N = Molecular weight x H equi per mole X L solution
(2.4)
CHE 401 : ANALYTICAL CHEMISTRY CHE 401 : ANALYTICAL CHEMISTRY

2.4.6 Solution-diluent ratio

2.4.4 Percent concentration
The composition of a dilute solution is sometimes specified in terms of the volume of a more
Percent composition of a solution can be expressed in several ways. Three common methods are 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.
weight solute
weight percent(w⁄w) = x 100% (2-5)
weight solution
Thus, a 1:4 HCI solution contains four volumes of water for each volume of concentrated
volume solute
hydrochloric acid.
volume percent(v⁄v) = x 100% (2-6)
volume solution
This method of notation is frequently ambiguous in that the concentration of the original solution
is not always obvious to the reader.
weight solute, g
weight/volume percent(w⁄v) = x 100% (2.7)
volume solution, mL
Moreover, under some circumstances 1:4 means dilute one volume with three volumes. Because
of such uncertainties, you should avoid using solution-diluent ratios.
2.4.5 Parts per million and parts per billion

For very dilute solutions. parts per million (ppm) is a convenient way to express concentration: 2.4.7 P-Functions

mass of solute Scientists frequently express the concentration of a species in terms of its p-function, or p-value.
cppm = x 106 ppm (2.8) The p-value is the negative logarithm (to the base 10) of the molar concentration of that species.
mass of solution
Thus, for the species X,
where Cppm is the concentration in parts per million. Obviously, the units of mass in the numerator and
denominator must agree. For even more dilute solutions, 109 ppb rather than 106 ppm is employed in the pX = -log [X] (2.9)
foregoing equation to give the results in parts per billion (ppb). The term parts per thousand (ppt) is also
encountered, especially in oceanography. As shown by the following examples, 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.
Example 2.8
What is the molarity of K+ in a solution that contains 63.3 ppm of K3Fe(CN)6(329.3 g/mol)?
Example 2.9
Because the solution is so dilute, it is reasonable to assume that its density is 1.00 g/mL. Therefore, Calculate the p-value for each ion in a solution that is 2.00 x 10-3 M in NaCl and
according to Equation 2.8. 5.4 x 10-4 M in HCl.
pH = -log [H+] = -log (5.4 x 10-4) = 3.27
63.3 ppm K3Fe(CN)6 = 63.3 mg K3Fe(CN)6 / L
To obtain pNa, we write
no. mol K 3 Fe(CN)6 63.3 mg K 3 Fe(CN)6 1 g K 3 Fe(CN)6 1 mol K 3 Fe(CN)6 pNa = -log (2.00 x 10-3) = -log 2.00 x 10-3 = 2.699
= × ×
L L 1000 mg K 3 Fe(CN)6 329.3g K 3 Fe(CN)6
The total Cl- concentration is given by the sum of the concentrations of the two solutes:
mol [Cl-] = 2.00 x 10-3 M + 5.4 x 10-4 M
= 1.922x10−4 = 1.922x10−4 M
L = 2.00 x 10-3 M +0.54 x 10-3 M = 2.54 x 10-3 M
pCl = -log 2.54 x 10-3 = 2.595
1.922x10−4 mol K 3 Fe(CN)6 3 molK + molK +
[K + ] = x = 5.77x10−4 = 5.77x10−4 M
L 1 mol K 3 Fe(CN)6 L
Example 2.10
Calculate the molar concentration of Ag+ in a solution that has a pAg of 6.372.

pAg = -log [Ag+] = 6.372

log [Ag+] = -6.372
[Ag+] = 4.246 x 10-7 = 4.25 x 10-7
CHE 401 : ANALYTICAL CHEMISTRY CHE 401 : ANALYTICAL CHEMISTRY

First calculate the molarity of the concentrated reagent. We then calculate the number of moles of
acid that we need for the diluted solution. Finally, we divide the second figure by the first to obtain
2.4.8 Density and specific gravity the volume of concentrated acid required.

Density expresses the mass of a substance per unit volume. In Thus, to obtain the molarity of the concentrated reagent, we write
SI units, density is expressed in units of kg/L or, alternatively, 1.18x103 g reagent 37g HCl 1 mol HCl
g/mL. cHCl = x x = 12.0 𝑀
L reagent 100g reagent 36.5 g HCl
Specific gravity is the ratio of the mass of a substance to The number of moles of HCl required is given by
the mass of an equal volume of water. 1L 6.0 mol HCl
no. mol HCl = 100 mL x x = 0.600 mol HCl
𝐝𝐞𝐧𝐬𝐢𝐭𝐲 𝐨𝐟 𝐭𝐡𝐞 𝐬𝐮𝐛𝐬𝐭𝐚𝐧𝐜𝐞 1000 mL L
𝐬𝐩𝐠𝐫 =
𝐝𝐞𝐧𝐬𝐢𝐭𝐲 𝐨𝐟 𝐰𝐚𝐭𝐞𝐫 𝐚𝐭 𝐫𝐞𝐟𝐞𝐫𝐞𝐧𝐜𝐞 𝐭𝐞𝐦𝐩𝐞𝐫𝐚𝐭𝐮𝐫𝐞
(2.10) Finally, to obtain the volume of concentrated reagent, we write

1 L reagent
vol concd reagent = 0.600 mol HCl x = 0.0500 L or 50.0 mL
Example 2.11 12.0 mol HCl
Calculate the molar concentration of HN03 (63.0
*Thus, dilute 50 mL of the concentrated reagent to 600 mL.
g/mol) in a solution that has a specific gravity of 1.42
and is 70.5% HN03 (w/w). Fig 2.1 Label of hydrochloric acid
Relationship of Volume and Concentration
Let us first calculate the grams of acid per liter of concentrated solution.
Vconc x Cconc = Vdil x Cdil (2.11)
g HNO3 1.42 kg reagent 103 g reagent 70.5 g HNO3 1001 g HNO3
= x x =
L reagent L reagent kg reagent 100g reagent L reagent

Then 2.5 CHEMICAL STOICHIOMETRY

1001 g HNO3 1 mol HNO3 15.9 mol HNO3 Stoichiometry is defined as the quantitative relationship among reacting chemical species.
cHNO3 = x = = 16 M
L reagent 63.0 g HNO3 L reagent

(1) (2) (3)

TABLE 2.3 Specific Gravities of Commercial Concentrated Acids and Bases mass moles moles mass
Reagent Concentration, % (w/w) Specific Gravity
Acetic acid 99.7 1.05
Ammonia 29.0 0.90
Divided by Multiply by Multiply by
Hydrochloric Acid 37.2 1.19
Hydrofluoric Acid 49.5 1.15 molar mass stoichiometric molar mass
Nitric Acid 70.5 1.42 ratio
Perchloric Acid 71.0 1.67 Fig 2.2 Flow diagram for making stoichiometric calculation
Phosphoric Acid 86.0 1.71
Sulfuric Acid 96.5 1.84
Empirical and Molecular formula
Example 2.12
An empirical formula gives the simplest whole number ratio of atoms in a chemical compound.
Describe the preparation of 100 mL of 6.0 M HO from a concentrated solution that has a specific
In contrast, a molecular formula specifies the number of atoms in a molecule. Two or more
gravity of 1.18 and is 37% (w/w) HCl (36.5 g/mol).
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
CHE 401 : ANALYTICAL CHEMISTRY CHE 401 : ANALYTICAL CHEMISTRY

the empirical formula for such diverse substances as acetic acid, C 2H4O2 glyceraldehyde, 275.7 g Ag 2 CO3
C3H6O3, and glucose, C6H12O6, as well as more than 50 other substances containing 6 or fewer mass AgNO3 = 0.02198 mol Ag 2 CO3 x = 6.06 g Ag 2 CO3
mol Ag 2 CO3
carbon atoms. The empirical formula is obtained from the percent composition of a compound.
The molecular formula requires, in addition, knowledge of the molar mass of the species. A Example 2.14
structural formula provides additional information. For example, the chemically different What mass of Ag2CO3 (275.7 g/mol) is formed when 25.0 mL of 0.200 M AgNO 3 are
ethanol and dimethyl ether share the same molecular formula C 2H6O. Their structural mixed with 50.0 mL of 0.0800 M Na2CO3?
formulas, C2H5OH and CH3OCH3, reveal structural differences between these compounds that
are not shown in their common molecular formula. Mixing these two solutions will result in one (and only one) of three possible outcomes,
specifically:
Stoichiometric Calculations (a) An excess of AgNO3 will remain after reaction is complete.
(b) An excess of Na2CO3 will remain after reaction is complete.
2NaI(aq) + Pb(NO3)2(aq) PbI2(s) + 2NaNO3(aq) (c) An excess of neither reagent will exist (that is. the number of moles of Na2CO3
is exactly equal to twice the number of moles of AgNO3).
It indicates that 2 mol of aqueous sodium iodide combine with 1 mol of aqueous lead nitrate to
produce 1 mol of solid lead iodide and 2 mol of aqueous sodium nitrate. As a first step, we must establish which of these situations applies by calculating
the amounts of reactants (in chemical units) available at the outset.
Example 2.13 demonstrates how the weight in grams of reactants and products in a chemical
reaction are related. As shown in Figure 2-2, a calculation of this type is a three-step process Initial amounts are
involving 1 L AgNO3 0.200 mol AgNO3
(1) transformation of the known mass of a substance in grams to a corresponding number amount of AgNO3 = nAgNO3 = 25.0 mL AgNO3 x x
1000 mL AgNO3 L AgNO3
of moles,
(2) multiplication by a factor that accounts for the stoichiometry, and = 5.00x10−3 mol AgNO3
(3) reconversion of the data in moles back to the metric units called for in the answer.
1 L Na2 CO3 0.0800 mol Na2 CO3
Example 2.13 no. mol Na2 CO3 = nNa2CO3 = 50.0 mL Na2 CO3 x x
1000 mL Na2 CO3 L Na2 CO3
(a) What mass of AgNO3 (169.9 g/mol) is needed to convert 2.33 g of Na 2CO3 (106.0
g/mol) to Ag2CO3? (b) What mass of Ag2CO3 (275.7 g/mol) will be formed?
= 4.00x10−3 mol Na2 CO3
(a) Na2CO3(aq) + 2AgNO3(aq) Ag2CO3(s) + 2NaNO3(aq)
Because each 𝐶𝑂𝟑𝟐− ion reacts with two Ag+ ions, 2 x 4.00 x 10-3 = 8.00 x 10-3 mol AgNO3 is
Step 1. required to react with the Na2CO3. Since we have insufficient AgNO3, situation (b) prevails and
1molNa2 CO3 the amount of Ag2CO3 produced will be limited by the amount of AgNO3 available. Thus,
no. mole Na2 CO3 = nNa2CO3 = 2.33 g Na2 CO3 x = 0.02198 mol Na2 CO3
106.0gNa2 CO3 1 mol Ag 2 CO3 275.7 g Ag 2 CO3
mass Ag 2 CO3 = 5.00x10−3 mol AgNO3 x x
Step 2. The balanced equation reveals that 2 mol AgNO3 mol Ag 2 CO3
2 mol AgNO3
no. mol AgNO3 = nAgNO3 = 0.02198 mol Na2 CO3 x = 0.689gAg 2 CO3
1 mol Na2 CO3
= 0.04396molAgNO3
Example 2.15
Here the stoichiometric factor is (2 mol AgNO3) / (1 mol Na2CO3).
What will be the analytical molar Na 2CO3 concentration in the solution produced when
25.0 mL of 0.200 M AgNO3 are mixed with 50.0 mL of 0.0800 M Na2CO3? We have seen
Step 3.
169.9 g AgNO3 in the previous example that formation of 5.00 X 10 -3 mol of AgNO3 will require 2.50 X
mass AgNO3 = 0.04396 mol AgNO3 x = 7.47 g AgNO3 10-3 mol of Na2CO3. The number of moles of unreacted Na2CO3 is then given by
mol AgNO3
1 mol Na2 CO3
no. mol Ag 2 CO3 = no. mol Na2 CO3 = 0.02198 mol nNa2 CO3 = 4.00 × 10−3 mol Na2 CO3 − 5.00 × 10−3 mol AgNO3 ×
2 mol AgNO3
CHE 401 : ANALYTICAL CHEMISTRY

= 1.50 × 10−3 𝑚𝑜𝑙 𝑁𝑎2 𝐶𝑂3

By definition the molarity is the number of moles of Na 2CO3/L. Thus,

1.50 × 10−3 mol Na2 CO3 100 ml
CNa2 CO3 = × = 0.0200 M Na2 CO3
(50 + 25) ml 1L

2.6 END OF MODULE TEST

Methods of expressing concentrations

1. What is the normality of the solution prepared by dissolving 25.2 grams oxalic acid
in sufficient water to give 1.2L of solution? What is the molarity of the solution?
Consider the density of water is 1.00 g/mL, calculate also the molarity.
2. What volume of 0.15N reagent is needed for the preparation of 500 mL of 0.10N
solution?
3. A sample of impure oxalic acid which weighs 0.4750 gram requires 35.6 mL of
0.20N NaOH. Calculate the percentage oxalic acid in the sample.
4. What is the normality of the solution prepared by dissolving 25.2 grams oxalic acid
in sufficient water to give 1.2L of
5. Calculate the p-functions for each ion in a solution that is
i. 0.020M in KCl
ii. 2.7 x 10-3M in Ca(OH)2
iii. 1.42 x 10-3M in CaCl2 and 2.5x10-3M in BaCl2
6. Describe the preparation of
i. 500 mL of 3.50% (w/v) aqueous glycerol
ii. 500 mL of 2.45%(v/v) aqueous ethanol
iii. 5.00L of 0.020M KMnO4 from solid reagent

Chemical Stoichiometry
When 50 mL of 0.250M NaI was added to 100 mL of 0.050M Pb(NO3)2, what is the
(a) mass of PbI2 formed in grams,
(b) mass of NaNO3 formed in grams,
(c) What is the excess reactant, how much in the grams is in excess?