SECTION 2: Laboratory Reagents and Solutions
2.1: Preparation of reagents
Introduction
The chemistry reagents play an important role in the correctness of an experiment in the
laboratory. If the composition of reagent is not correct, it often leads to errors in the
observations and results. While preparing the chemistry reagents in a laboratory,
correct proportion of chemicals and /or solvents as well as procedure is very crucial.
Safety is also very important, as Chemistry Labs are highly prone to accidents. While
preparing reagents, one should be aware of correct handling, procedure, storage and
safety hazards. With adequate knowledge and care, accidents can be avoided in the
laboratory while preparing reagents.
Quality of Chemicals
The quality of chemicals/solvents used in the analytical laboratory may vary from
laboratory grade to Analytical or Guaranteed Grade (Analar or AR or G.R.). The quality
of chemical/solvents may become one of the causes of analytical errors, may affect the
analytical instrument or may lead to interferences during determinations. Hence,
selection of laboratory chemicals of an appropriate quality is most important factor for
achieving result with desired accuracy. For preparation of all standard solutions only
―Analytical reagent grade (AR) or guaranteed reagent grade (GR) should be used,
since their purity levels are known. Commercially produced chemical reagents such as
acids and ammonia are highly concentrated solutions. For instance; commercial
concentrated Tetraoxosulphate (VI) acid, H2SO4 is approximately 18 – molar. In order to
prepare solutions of lower concentrations a calculated volume of the concentrated
solution is taken from the stock solution and then added to a specified volume of
distilled water. However the volume of such a solution to be taken depends on the
information provided by the manufacturer on the label pasted on the stock bottle. For
instance; the label on the stock bottle of concentrated H2SO4.
Table 2.1: Concentrated Liquid Analytical Reagents
Reagent %Purity R.M.M Specific Gravity
(g/mole) (S.G)
CH3COOH 99.5 60 1.05
NH3 35 17 0.88
HCl 36 36.5 1.18
NF 48 20 1.18
HNO3 70 63 1.42
HClO3 60 84.5 1.53
H3PO4 85 98 1.69
H2SO4 98 98 1.80
From Table 2.1, taking HCl for example:
The specific gravity of 1.18 means that the stock solution is 1.18 times heavier than an
equal volume of water; i.e. 1cm3 of the stock acid solution weighs 1.18g or 1000cm3
(1dm3 ) of stock solution weighs 1.18 x 1000 = 1180g.
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The 36% by mass means: 36g of the acid (solute) is in 100g of solution i.e. 100g of
stock solution contains 36g of HCl. 1180g (mass of 1dm 3 of solution) contains (36/100)
X 1180 = 424.8g. i.e. 1dm3 of stock solution contains 424.8g of pure HCl, therefore its
mass concentration = 424.8g/dm3.
Hence, its molar concentration, C = 424.8g per dm3 /36g per mole = 11.8 mole per dm3
i.e. the concentration of the stock solution is 11.8 molar HCl.
General Instructions in preparing laboratory reagents
It is highly recommended that the following precautions must be duly followed while
preparing the reagents.
Always wear a lab-coat and safety goggles.
Wear disposable gloves while dealing with highly poisonous/irritant chemicals.
Follow the specific procedure and amounts/volumes of chemicals and solvents to be
used for the reagent to be prepared.
Use clean and dry glass apparatus while preparing the reagents.
Store the reagents after proper labeling (name of reagent, date of preparation, hazard
warning) as per the instructions in clean apparatus.
Dispose of any waste paper or any kind of solid waste properly.
Maintain a safe distance while using the chemicals.
Never touch, taste, or smell any chemical, whatever it may be.
Make sure no flammable solvents are in the surrounding area when lighting a
matchstick or a burner.
Hold containers away from the body when transferring a chemical or solution from one
container to another.
Add concentrated acid to water slowly. Never add water to a concentrated acid.
Exercise 2.1
1. Determine the concentration of the stock solution of H2SO4 and CH3COOH
2. What are the different qualities of chemicals/solvents used in the analytical
laboratory? Which of these is best for preparation of standard solutions and why?
3. What precaution should be taken in mixing concentrated acid with water?
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2.2: Reagent preparation from stock standard solution
Introduction
Analysis in any laboratory is mainly based on reference materials like Stock standard
solution. The accuracy in the preparation of stock standard reflects accuracy of the
results
Definition of Some Terms
Stock standard solution is defined as a solution with high concentration of stable
analyte(s) that can be stored at specific conditions in laboratory for long time and used
as a standard reference material for analysis of the target analyte(s) in the daily use.
Standard solution is a solution of known concentration e.g. 0.5 Molar H2SO4.
Molar solution is a solution that contains 1 mole of solute per litre (1 dm 3 ) e.g. A molar
solution of NaOH can be prepared by dissolving 1 mole (40 g) of NaOH (Na = 23, O =
16, H =1) in 1 litre of distilled water. Therefore 80 g of NaOH will be required in 1 litre of
distilled water to prepare 2 molar NaOH solution.
Expressing Concentration of Solute:
Concentration is a general measurement unit stating the amount of solute present in a
known amount of solution:
Although the terms Solute and Solution are often associated with liquid samples, they
can be extended to gas-phase and solid-phase samples as well. The actual units for
reporting concentration depend on how the amount of solute and solution are
measured.
Molarity and Formality
Both molarity and formality express concentration as moles of solute per liter of solution.
There is, however, a subtle difference between molarity and formality. Molarity is the
concentration of a particular chemical species in solution. Formality, on the other hand,
is a substance‘s total concentration in solution without regard to its specific chemical
form. There is no difference between a substance‘s molarity and formality if it dissolves
without dissociating into ions. The molar concentration of a solution of glucose, for
example, is the same as its formality.
For substances that ionize in solution, such as NaCl, molarity and formality are different.
For example, dissolving 0.1 mol of NaCl in 1 L of water gives a solution containing 0.1
mol of Na+ and 0.1mol of Cl– . The molarity of NaCl, therefore, is zero since there is
essentially no undissociated NaCl in solution. The solution, instead, is 0.1 M in Na+ and
0.1 M in Cl– . The formality of NaCl, however, is 0.1F because it represents the total
amount of NaCl in solution. The rigorous definition of molarity, for better or worse is
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largely ignored in the current literature, as it is in this text. When we state that a solution
is 0.1 M NaCl we understand it to consist of Na+ and Cl– ions. The unit of formality is
used only when it provides a clearer description of solution chemistry.
Molar concentrations are used so frequently that a symbolic notation is often used to
simplify its expression in equations and writing. The use of square brackets around a
species indicates that we are referring to that species‘ molar concentration. Thus, [Na + ]
is read as the molar concentration of sodium ions
Note that it is the final volume of the solution that is important, not the starting volume of
the solvent used. The final volume of the solution might be a bit larger than the volume
of the solvent because of the additional volume of the solute. In practice, a solution of
known molarity is prepared by weighing an appropriate amount of solute and placing it
in a volumetric flask. Enough solvent is added to dissolve the solute, and further solvent
is added until an accurately calibrated final volume is reached.
Preparing a stock solution of known molarity
(a) A measured number of moles of solute is weighed using analytical balance.
(b) Solute is transferred in a volumetric flask.
(c) Enough solvent is added to dissolve the solute by swirling and further solvent is
carefully added until the calibration mark on the neck of the flask is reached, and the
solution is then shaken until uniform. Molarity can be used as a conversion factor to
relate a solution‘s volume to the number of moles of solute. If we know the molarity
and volume of a solution, we can calculate the number of moles of solute. If we
know the number of moles of solute and the molarity of the solution, we can find the
solution‘s volume.
Examples 1. What is the molarity of a solution made by dissolving 2.355 g of sulfuric
acid in water and diluting to a final volume of 50.0 mL?
Solution
Molarity is the number of moles of solute per liter of solution. Thus it‘s necessary to find
the number of moles of sulfuric acid in 2.355 g and then divide by the volume of the
solution. Molar mass of H2SO4 = (2 x 1.0 g/mol) + (1 x 32.1 g/mol) + (4 x 16.0 g/mol) =
98.1 g/mol
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The solution has a sulfuric acid concentration of 0.480 M
Normality
Normality is an older unit of concentration that, although once commonly used, is
frequently ignored in today‘s laboratories. Normality is still used in some handbooks of
analytical methods, and, for this reason, it is helpful to understand its meaning. For
example, normality is the concentration unit used in Standard Methods for the
Examination of Water and Wastewater, and in some Standard EPA methods commonly
used sources of analytical methods for environmental laboratories. Normality makes
use of the chemical equivalent, which is the amount of one chemical species reacting
stoichiometrically with another chemical species. Note that this definition makes an
equivalent, and thus normality, a function of the chemical reaction in which the species
participates. Although a solution of H2SO4 has a fixed molarity, its normality depends on
how it reacts.
The number of equivalents, n, is based on a reaction unit, which is that part of a
chemical species involved in a reaction. In a precipitation reaction, for example, the
reaction unit is the charge of the cation or anion involved in the reaction; thus for the
reaction
Pb2+(aq) + 2I– (aq) PbI2(s)
n = 2 for Pb2+ because each ion takes two electrons and n = 1 for I because each ion
donate only one electron. In an acid–base reaction, the reaction unit is the number of H+
ions donated by an acid or accepted by a base. For the reaction between sulfuric acid
and ammonia
H2SO4(aq) + 2NH3(aq) 2NH4 + (aq) + SO4 2– (aq)
we find that n = 2 for H2SO4 because each molecule donate two ions of H+ and n = 1 for
NH3 because each ion accept one H+. For a complexation reaction, the reaction unit is
the number of electron pairs that can be accepted by the metal or donated by the
ligand. In the reaction between Ag+ and NH3
Ag+ (aq) + 2NH3 (aq) Ag(NH3) 2+ (aq)
the value of n for Ag+ is 2 because each ion accept pair of electrons in covalent bonds
with AmmoniaNH3 one electron from each covalent bond, for NH3 is n = 1 because each
molecule of ammonia donate one electron in each covalent bond it form with Ag+ .
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Finally, in an oxidation–reduction reaction there action unit is the number of electrons
released by the reducing agent or accepted by the oxidizing agent; thus, for the reaction
2Fe3+ (aq) + Sn2+ (aq) Sn4+ (aq) + 2Fe2+ (aq)
n = 1 for Fe3+ because each ion accept one electron in the reduction step and n = 2 for
Sn2+ because each ion donate two electrons in the oxidation step. Clearly, determining
the number of equivalents for a chemical species requires an understanding of how it
reacts. Normality is the number of equivalent weights (EW) per unit volume and, like
formality, is independent of speciation. An equivalent weight is defined as the ratio of a
chemical species‘ formula weight (FW) to the number of its equivalents.
Consequently, the following simple relationship exists between normality and molarity.
N=nxM
This equation is the simple form to fully understand the normality, you have to be able to
determine the number of equivalents and calculate the molarity then use above
equation to calculate the normality of the target analyte.
Molality
Molality is used in thermodynamic calculations where a temperature independent unit of
concentration is needed. Molarity, formality and normality are based on the volume of
solution in which the solute is dissolved. Since density is a temperature dependent
property a solution‘s volume, and thus it‘s molar, formal and normal concentrations, will
change as a function of its temperature. By using the solvent‘s mass in place of its
volume, the resulting concentration becomes independent of temperature. Molality is
defined as mole of solute in Kg of solvent as per equation:
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Exercise 2.2
1. Differentiate between molarity and Normality
2.3: Converting between concentration units
Introduction
Many scientific activities involve numerical calculations - measuring, weighing,
preparing solutions, and so forth—and it‘s often necessary to convert a quantity from
one unit to another. The simplest way to carry out calculations that involve different
units is to use the dimensional-analysis method.
Dimensional analysis method
In this method, a quantity described in one unit is converted into an equivalent quantity
with a different unit by using a conversion factor to express the relationship between
units:
As an example, we know that 1 ppm equals 1000 ppb. Writing this relationship as a
fraction restates it in the form of a conversion factor, either ppm per ppb or ppb per
ppm:
Conversion factor between ppm and ppb
= = 1
Note that this and all other conversion factors are numerically equal to 1 because the
value of the quantity above the division line (the numerator) is equal to the value of the
quantity below the division line (the denominator). Thus, multiplying by a conversion
factor is equivalent to multiplying by 1 and so does not change the value of the quantity.
The key to the dimensional-analysis method of problem solving is that units are treated
like numbers and can thus be multiplied and divided (though not added or subtracted)
just as numbers can. The idea when solving a problem is to set up an equation so that
unwanted units cancel, leaving only the desired units. Usually it‘s best to start by writing
what you know and then manipulating that known quantity.
For example, if you know the volume is 121 mL and want to find it in deciliter (dL), you
can write down the volume in mL and set up an equation multiplying the mL by the
conversion factor in mL per dL:
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The unit ―mL cancels from the left side of the equation because it appears both above
and below the division line, and the only unit that remains is ―dL The dimensional-
analysis method gives the right answer only if the equation is set up so that the
unwanted units cancel. The main drawback to using the dimensional-analysis method is
that it‘s easy to get the right answer without really understanding what you‘re doing. It‘s
therefore best after solving a problem to think through a rough estimate, or ―ballpark‖
solution, as a check on your work. If your ballpark check isn‘t close to the detailed
solution, there‘s a misunderstanding somewhere, and you should think the problem
through again. Even if you don‘t make an estimate, it‘s important to be sure that your
calculated answer makes sense. The dimensional-analysis method and the use of
ballpark checks are techniques that will help you solve problems of many kinds, not just
unit conversions. Conversion between concentration units is so easy once you
understand the above conversion principles, the units of concentration most frequently
encountered in analytical chemistry are molarity, weight percent, volume percent,
weight-to-volume percent, parts per million, and parts per billion. By recognizing the
general definition of concentration given, it is easy to convert between concentration
units. Table 2.1 shows relations between most commonly volume units.
Table 2.1: Conversion between commonly used volume units
Unit Symbol Relation Remark
Liter L 1 L = 1000 mL
Deciliter dL 1 dL = 100 mL deci = 10-1
1 L = 10 dL deciLiter = 10-1 L
Milliliter mL 1 L = 1000 mL milli = 10-3
1 dL = 100 mL milliLiter = 10-3 L
Cubic meter m3 1 m3 = 1000 L
1 m3 = 10, 000 dL
Cubic decimeter dm3 1 m3 = 1000 dm3 deci = 10-1
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1 m = 1000 L deci…)3 = 10-3
1 dm3 = 1 L Cubic decimeter = 10-3 m3
Cubic Centimeter cm3 1 m3 = 1000 dm3 centi = 10-2
1 dm3 = 1000 cm3 (centi…)3 = 10-6
1 L = 1 dm3 Cubic centimeter = 10-6 m3
1 L = 1000 mL
1 mL = 1 cm3
Dilution of Concentrated Solutions
Dilution is one of the main preparation processes which used daily in all laboratories;
any chemist should be familiar with dilution calculations to prepare a correct diluted
solution. For convenience, chemicals are sometimes bought and stored as concentrated
solutions that must be diluted before use. Aqueous hydrochloric acid, for example, is
sold commercially as a 12.0 M solution, yet it is most commonly used in the laboratory
after dilution with water to a final concentration of 6.0 M or 1.0 M.
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The key fact to remember when diluting a concentrated solution is that the number of
moles of solute is constant; only the volume is changed by adding more solvent.
Because the number of moles of solute can be calculated by multiplying molarity times
volume, we can set up the following equation:
Where Mi is the initial molarity, Vi is the initial volume, Mf is the final molarity, and Vf is
the final volume after dilution. Rearranging this equation into a more useful form shows
that the molar concentration after dilution (Mf) can be found by multiplying the initial
concentration (Mi) by the ratio of initial and final volumes (Vi/Vf)
Vf/Vi is called Dilution Factor
Example
Dilute 20.0 mL of a solution of 2.00 M to a volume of 100.0 mL. The solution volume
increases by a factor of five (from 20 mL to 100 mL), so the concentration of the solution
must decrease by a factor of five (from 2.00 M to 0.400 M):
Exercise 2.3
1. How do you prepare a 200 mL solution of 2.0 M Sulfuric acid (H 2SO4) from
concentrated bottle of Sulfuric acid. If the following information written on Sulfuric
acid bottle: M. Wt = 98.08 g/mol, S.G= 1.84 g/cm3, 97% (w/w).
2. How would you prepare 250.0 mL of 0.500 M NaOH solution starting from a
concentration of 1.000M?
