STOICHIOMETRIC CALCULATIONS

▪ Analytical chemistry deals with measurements of analytes in solids and

concentrations in solution.
▪ We prepare solutions of known concentrations that can be used to calibrate
instruments or to titrate sample solutions.
▪ We calculate the mass of an analyte in a solution from its concentration and the
volume.
▪ We calculate the mass of product expected from the mass of reactants.
✓ All of these calculations require a knowledge of stoichiometry, that is, the ratios in
which chemicals react, from which we apply appropriate conversion factors to
arrive at the desired calculated results.
▪ A solution is a homogenous mixture of two or more chemical
substances.
▪ Homogeneous means that the composition of the mixture is identical
throughout the solution.
▪ The minor component is generally known as the solute, while the
bulk component is called the solvent.
▪ Concentration is the quantity of solute in a specified volume or mass
of solution or solvent.
▪ The concentrations of solutes can be expressed in various ways.
▪ The molar concentration of a solution containing a species X is the number of
moles of the species that is contained in one liter of solution.
▪ The unit for molar concentration is molarity, M or mol/L.
▪ It can also e expressed as the no of millimoles of solutes per milliliter of solution.

Molar concentration = no of mol solute

no L solution

= no mmol solute
no mL solution
▪ There are two versions of molarity, namely analytical molarity and species molarity.
▪ The analytical molarity refers to the total number of moles of the solute in one liter
of solution.
▪ It describes how a solution of a given molarity can be prepared.
▪ For example, 0.1 M of hydrochloric acid solution can be prepared by dissolving 1
mol of HCl in water and diluting to exactly 1.0 L.
▪ Species molarity is the concentration that can be expressed as the number of
moles of a particular species in one liter of a solution at equilibrium.
▪ The concentration unit is usually written in brackets.
▪ For example, [H+] means the concentration of H+.
▪ The behavior or degree of ionization f the dissolved solutes should be known.
▪ Chemist sometimes use the term formality or formal concentration to distinguish
the two types of molarity; formal concentration for analytical concentration and
molar concentration for species concentration.
▪ Operationally, formality is identical to molarity.
▪ Formality is expressed as the number of formula weights per liter of solution.
▪ Molality (m) is a concentration expressed as the number of
moles of the substance per kilograms of the solvent (not the total
solution)
▪ Typical seawaters contain sodium chloride, NaCl as much as 2.7 g per 100 mL.

(a) What is the molarity of NaCl in the saline water?

(b) The MgCl2 content of the saline water is 0.054 M. Determine the weight (grams)
of MgCl2 in 50 mL of the saline water?
▪ Although molarity is widely used in chemistry, some chemist use a
unit of concentration in quantitative analysis called normality (N).
▪ A one-normal solution contains one equivalent per liter.

▪ The normality of a solution is the number of moles of reacting units

per litre. One reacting unit is called one equivalent.
▪ A reacting unit is a proton or an electron.

▪ The number of equivalents is given by the number of moles

multiplied by the number of reacting units per molecule or atom.
N = nM
▪ The equivalent weight is the formula weight divided by the number
or reacting units.
▪ For example, sulfuric acid, H2SO4, has two reacting units of protons;
that is there are two equivalents of protons in each mole.
▪ Therefore, equivalent weight = 98.08 g/mol = 49.04 g/eq

2 eq/mol
▪ The composition of materials that are composed of more than one
pure element or a single pure compound can be expressed in terms
of percent composition.
▪ The main types are weight-to-weight, weight-to-volume, volume-to-
volume.
mass of solute
▪ Weight percent, % w/w = x 100
weight of solution or mixture

▪ For example, ethanol is usually supplied as in a concentration of 95%

(w/w). It means that 100 g of the solution contains 95 g of ethanol.
▪ Volume percent (% v/v) is sometimes used to expressed the composition of solute:
volume of solute
▪ Volume percent, % v/v = x 100
volume of solution

▪ The weight-to-volume percent (% w/v) can be used to expressed the composition

of solute:

mass of solute
▪ Weight to volume, % w/v = x 100
volume of solution
▪ The weight-to-weight unit can also be expressed s a fraction.
▪ For example, 23% (w/w) can be expressed as 23 parts per hundred (pph).
▪ Smaller fractions are expressed in parts per million (ppm), parts per billion (ppb)
and parts per trillion (ppt). These units of concentrations are usually used to
expressed very low concentrations.
▪ Parts per million (ppm) is grams of solute per million grams of total solution
or mixture.
▪ Parts per billion (ppb) means grams of solute per billion grams of total
solution or mixture.
▪ Parts per trillion (ppt) is grams per trillion grams of total solution or
mixture.
▪ As the density of aqueous solutions is often very close to 1.00 g/L, we
usually use correlate 1 g of water with 1 mL of water, although it is only a
close approximation. Therefore,
▪ 1 ppm = 1 μg/ mL = 1mg/ L
▪ 1 ppb = 1 ng/mL = 1 μg/ L
A solution contains 118.5 g KI per liter of solution. Calculate the concentration in (a)
% (w/v) and (b) % (w/w). Given the density of the solution at 25℃ is 1.078 g / mL

118.5 g /1000 ml X 1 ml/1.078 g

▪ An aqueous solution (10.0 mL) contains 56 ppm SO2. Calculate the molarity of the
solution.
▪ As a student, you are given cupric sulfate pentahydrate (CuSO4.5H2O, MW 249.69
g/mol). Describe how you can prepare a 500 mL standard solution of 10.00 mM
Cu2+ from the reagent.
▪ You are given an EDTA, (C10H16N2O8) MW 292.25 g/mol) sample that has 99.5%
purity. Describe how you can prepare a 1000 mL of standard solution of 0.0100 M
EDTA solution using the regent.
▪ Dilute solution (with low concentration) can be prepared from a
more concentrated solution.
▪ A known volume of the concentrated solution can be transferred
into a new flask and diluted to the required volume or weight.
▪ Number of mol = M x V
▪ The number of moles of analyte in the solution equals to the number
of moles of analyte in the transferred concentrated solution. Hence,
▪ M1 x V1 = M2 x V2
▪ Where;
M1 Initial concentration of solution
M2 Concentration of final solution
V1 Volume of concentrated solution transferred
V2 Final volume of the dilute solution formed
▪ The laboratory grade concentrated hydrochloric acid has a concentration of 12.1
M. What volume of the concentrated acid is necessary to prepare 500 mL of 0.100 M
HCl?
The solution formed when ammonia is dissolved in water is known as ammonium
hydroxide. In the solution, ammonia undergoes 72.0% (w/w) dissociation to achieve
the following equilibrium:
NH3 + H2O NH4+ + OH-

The density of concentrated NH4OH solution is 0.899 g/mL. Determine the volume of
the reagent that should be diluted to prepare a 500 mL solution of 0.100 M NH3.
▪ Volumetric or titrimetric analyses are among the most useful and accurate
analytical techniques, especially for millimole amounts of analyte.
▪ manual titrations nowadays are generally used only in situations that require high
accuracy for relatively small numbers of samples. They are used, for example, to
calibrate or validate more routine instrumental methods.
▪ Automated titrations are useful when large numbers of samples must be processed.
(A titration may be automated, for instance, by means of a color change or a pH
change that activates a motor-driven buret to stop delivery.
▪ The volume delivered may be electronically registered.
▪ The volumetric relationship may be used for calculating quantitative information
about the titrated analyte.
▪ In a titration, the test substance (analyte) reacts with an added reagent of known
concentration, generally instantaneously.
▪ The reagent of known concentration is referred to as a standard solution. It is
typically delivered from a buret; the solution delivered by the buret is called the
titrant.
▪ In some instances, the reverse may also be carried out where a known volume of
the standard solution is taken and it is titrated with the analyte of unknown
concentration as the titrant.
▪ The volume of titrant required to just completely react with the analyte is measured.
▪ Since we know the reagent concentration as well as the reaction stoichiometry
between the analyte and the reagent, we can calculate the amount of analyte.
The requirements of a titration are as follows:
▪ A standard solution is prepared by dissolving an accurately weighed quantity of a
highly pure material called a primary standard and diluting to an accurately
known volume in a volumetric flask.
▪ Alternatively, if the material is not sufficiently pure, a solution is prepared to give
approximately the desired concentration, and this is standardized by titrating a
weighed quantity of a primary standard.
▪ For example, sodium hydroxide is not sufficiently pure to prepare a standard
solution directly. It is therefore standardized by titrating a primary standard acid,
such as potassium acid phthalate (KHP). KHP is a solid that can be weighed
accurately.
▪ A solution standardized by titrating a primary standard is itself a secondary
standard. It will be less accurate than a primary standard solution due to the errors
of titrations.
A primary standard should fulfill these requirements:
There are four general classes of volumetric or titrimetric methods.
▪ Acid–Base

▪ Precipitation

▪ Complexometric

▪ Reduction–Oxidation
Assume 25.0mL of 0.100 M AgNO3 is required to titrate a sample containing sodium chloride.
The reaction is

Since Ag+ and Cl− react on a 1:1 molar basis, the number of millimoles of Cl− is
equal to the number of millimoles of Ag + needed for titration. We can calculate the
milligrams of NaCl as follows:
A 0.4671-g sample containing sodium bicarbonate was dissolved and titrated with
standard 0.1067 M hydrochloric acid solution, requiring 40.72 mL. The reaction is

Calculate the percent sodium bicarbonate in the sample.

▪ Many substances do not react on the basis of 1:1 mole ratio
▪ Consider the general reaction:
A 0.2638-g soda ash sample is analyzed by titrating the sodium carbonate with
the standard 0.1288 M hydrochloride solution, requiring 38.27 mL. The reaction is

Calculate the percent sodium carbonate in the sample.

How many milliliters of 0.25 M solution of H2SO4 will react with 10mL of a 0.25 M
solution of NaOH?
▪ When a titrant material of high or known purity is not available, the concentration
of the approximately prepared titrant solution must be accurately determined by
standardization; that is, by titrating an accurately weighed quantity (a known
number of millimoles) of a primary standard. From the volume of titrant used to
titrate the primary standard, we can calculate the molar concentration of the titrant.
Or, combining all steps at once,
▪ An approximate 0.1 M hydrochloric acid solution is prepared by 120-fold dilution
of concentrated hydrochloric acid. It is standardized by titrating 0.1876 g of dried
primary standard sodium carbonate:

▪ The titration required 35.86mL acid. Calculate the molar concentration of the
hydrochloric acid.
▪ Sometimes a reaction is slow to go to completion, and a sharp end point cannot be
obtained.
▪ In this technique, a measured amount of the reagent, which would normally be the
titrant, is added to the sample so that there is a slight excess. After the reaction with
the analyte is allowed to go to completion, the amount of excess (unreacted)
reagent is determined by titration with another standard solution; the kinetics of the
analyte reaction may be increased in the presence of excess reagent.
▪ So by knowing the number of millimoles of reagent taken and by measuring the
number of millimoles remaining unreacted, we can calculate the number of
millimoles of sample that reacted with the reagent
▪ Chromium(III) is slow to react with EDTA (H4Y) and is therefore determined by
back-titration. Chromium(III) picolinate, Cr(C6H4NO2)3, is sold as a nutritional
supplement for athletes with the claim that it aids muscle building. A nutraceutical
preparation containing chromium(III) is analyzed by treating a 2.63-g sample with
5.00mL of 0.0103 M EDTA. Following reaction, the unreacted EDTA is back-titrated
with 1.32mL of 0.0122 M zinc solution. What is the percent chromium picolinate in
the pharmaceutical preparation?
▪ For routine titrations, it is often convenient to calculate the titer of the titrant. The
titer is the weight of analyte that is chemically equivalent to 1mL of the titrant,
usually expressed in milligrams. For example, if a potassium dichromate solution
has a titer of 1.267 mg Fe, each milliliter potassium dichromate will react with 1.267
mg iron, and the weight of iron titrated is obtained by simply multiplying the
volume of titrant used by the titer. The titer can be expressed in terms of any form
of the analyte desired, for example, milligrams FeO or Fe2O3.
▪ A standard solution of potassium dichromate contains 5.442 g/L. What is its titer in
terms of milligrams Fe3O4?
▪ In gravimetric analysis the analyte is converted into an insoluble form.
▪ The precipitate is dried and weighed
▪ From the weight of the precipitate formed and the weight relationship between the
analyte and the precipitate, the weight of the analyte is calculated.
▪ Gravimetric factor is the weight of analyte per unit weight of precipitate. OR
▪ The ratio of the formula weight of the substance sought to that of the
substance weighed.

Wt of substance sought = wt of precipitate (substance weighed) X GF

▪ Calculate the weight of barium and the weight of Cl present in 25.0 g BaCl2.