Quantitative Chemical Analysis

Quantitative chemical analysis, branch of chemistry that deals with the determination of the
amount or percentage of one or more constituents of a sample.

A variety of methods is employed for quantitative analyses, which for convenience may be
broadly classified as chemical or physical, depending upon which properties are utilized.

Chemical methods depend upon such reactions as precipitation, neutralization, oxidation, or, in
general, the formation of a new compound. The major types of strictly chemical methods are
known as gravimetric analysis and volumetric, or titrimetric analysis.

Physical methods involve the measurement of some physical property such as density, refractive
index, absorption or polarization of light, electromotive force, magnetic susceptibility, and
numerous others. An analysis will often require a combination of methods: qualitative for
separating desired constituents from a sample and quantitative for measuring the amounts
present.

The principles and methods that enables us to measure “how much” is called quantitative
analysis. Quantitative chemical analysis measure how much chemical in a sample. The goal of
analytical chemist is to use this knowledge of “how much” for greater purpose, such as in
scientific investigation, a policy decision, a cost analysis, philosophical satisfaction or myriads
other reasons.

Solution Definition

In chemistry, a solution is a special type of homogeneous mixture composed of two or more

substances. In such a mixture, a solute is a substance dissolved in another substance, known as a
solvent. The solvent is the major component of a solution (the part that does the dissolving). The
solute is the minor component of the solution (the part that gets dissolved).

Expression of Concentrations
The SI unit (Systeme International d’Unites) of volume (which has the dimensions length 3) is
the cubic meter (m3). The common unit of volume is liter (L), which is defined as the volume of
a cube 0.1 m on each edge. The milliliter (mL; 1 mL= 10-3 L) is exactly 1 cm3. Small scale work
especially in biochemistry, often employs microliter (µL; 1 µL = 10-6L) volume.
Concentration signifies how much of a substance is contained in a specified volume/mass.
Concentration refers to the amount of solute that is dissolved in a solvent. We normally think of
a solute as a solid that is added to a solvent (e.g., adding table salt to water), but the solute could
easily exist in another phase. For example, if we add a small amount of ethanol to water, then the
ethanol is the solute, and the water is the solvent. If we add a smaller amount of water to a larger
amount of ethanol, then the water could be the solute.
Once you have identified the solute and solvent in a solution, you are ready to determine its
concentration. Concentration may be expressed several different ways, using percent
composition by mass, volume percent, mole fraction, molarity, molality, or normality.
Percent Composition by Mass (%)
This is the mass of the solute divided by the mass of the solution (mass of solute plus mass of
solvent), multiplied by 100.
Example:
Determine the percent composition by mass of a 100 g salt solution which contains 20 g salt.
Solution:
20 g NaCl / 100 g solution x 100 = 20% NaCl solution
Example: Seawater has 904ppm of sulfur. What is the mass percent of sulfur in seawater?
Assume one million of grams of seawater. The number of grams of solute in one million grams is
904. This gives
Mass % = (904g/1 x 106 g) x 100 = 0.0904%
Mass/mass percentages are the best ways of expressing concentrations for applications in which
the physical rather than the chemical properties of the mixture are most important. This is a poor
way of expressing concentration for solutions used in chemical reactions because the mole ratio
information is buried. We can convert the information to moles using the formula weight if
necessary.
Volume Percent (% v/v)
Volume percent or volume/volume percent most often is used when preparing solutions of
liquids. Volume percent is defined as:
v/v % = [(volume of solute)/(volume of solution)] x 100%
Note that volume percent is relative to the volume of the solution, not the volume of solvent. For
example, wine is about 12% v/v ethanol. This means there is 12 ml ethanol for every 100 ml of
wine.
Mole Fraction (X)
This is the number of moles of a compound divided by the total number of moles of all chemical
species in the solution. Keep in mind, the sum of all mole fractions in a solution always equals 1.
Example: What are the mole fractions of the components of the solution formed when 92 g
glycerol is mixed with 90 g water? (molecular weight of water = 18; molecular weight of
glycerol = 92)
Solution:
90 g water = 90 g x 1 mol / 18 g = 5 mol water
92 g glycerol = 92 g x 1 mol / 92 g = 1 mol glycerol
total mol = 5 + 1 = 6 mol
xwater = 5 mol / 6 mol = 0.833
x glycerol = 1 mol / 6 mol = 0.167
It's a good idea to check your math by making sure the mole fractions add up to 1:
xwater + xglycerol = .833 + 0.167 = 1.000
Example 2
Dentist’s amalgam is 70% mercury and 30% copper by mass. What is the mole fraction of
copper in dentist’s amalgam?
Solution
Note that the mole fraction of the components must be 1
Molar mass of Hg = 200.59g/mol; Molar mass of Cu = 63.546g/mol
Assume 100g of amalgam
No of mole of Hg = 70g/200.59 g/mol = 0.35 mol
No of mole of Cu = 30g /63.546g/mol = 0.47mol
By definition mole fraction of each component = no of mole of each component/ total no of
moles of the components
XCu = 0.47mol / 0.47mol + 0.35mol= 0.47 mol / 0.82 mol = 0.57 mol
For Hg
XHg = 0.35mol / 0.82 mol = 0.427 = 0.43
If the mole fraction of the components must be one, then add XCu + XHg = 0.57 + 0.43 + 1
Molarity (M)
Molarity is probably the most commonly used unit of concentration. It is the number of moles of
solute per liter of solution (not necessarily the same as the volume of solvent!).
Example 1:
What is the molarity of a solution made when water is added to 11 g CaCl2 to make 100 mL of
solution? (The molecular weight of CaCl2 = 110)
Solution:
Molarity = No of moles/ Volume
No of mole = Mass given / molar mass
Therefore, no of moles of CaCl2 = 11 g CaCl2 / 110 g / mol CaCl2) = 0.10 mol CaCl2
Volume given is in mL, convert to liter
100 mL x 1 L / 1000 mL = 0.10 L
molarity = 0.10 mol / 0.10 L
molarity = 1.0 M
Example 2
A solution contains 5.7 g of potassium nitrate dissolved in enough water to make 233 mL of
solution. What is its molarity?
Formula weight or Molar mass of KNO3 = 101.103 g/mol
No of moles of KNO3 = 57g/ 101.103gmol- = 0.056 mol
M = 0.056mol/ 0.233 L = 0.24 mol/L
Molality (m)
Molality is the number of moles of solute per kilogram of solvent. Because the density of water
at 25°C is about 1 kilogram per liter, molality is approximately equal to molarity for dilute
aqueous solutions at this temperature. This is a useful approximation, but remember that it is
only an approximation and doesn't apply when the solution is at a different temperature, isn't
dilute, or uses a solvent other than water. This is useful when the properties of the solvent are
being studied rather than the properties of the solute.
Unit = no of moles /kg
Example:
What is the molality of a solution of 10 g NaOH in 500 g water? (Molecular weight of NaOH is
40)
Solution:
 No of moles of NaOH = 10 g NaOH / (40 g mol – of NaOH) = 0.25 mol NaOH
Convert g to Kg = 500 g water x 1 kg / 1000 g = 0.50 kg water
molality = 0.25 mol / 0.50 kg
molality = 0.05 M / kg
molality = 0.50 m
Example 2
100g of amalgam contains 70 g of mercury and 30g of copper. What is the molality of mercury
in the amalgam/
m = 0.47mol/ 0. 070kg = 6.7mol/kg = 6.7m
Normality (N)
Normality, N, is similar to molarity, moles of solute per liter of solution. However, instead of the
entire solute, the normality is based on the number of moles of the active part of the solute,
called a chemical equivalent. For an acid, the chemical equivalent is the number of moles of H+
ion. For a base, the chemical equivalent is the no of OH- ions. For oxidation – reduction solution,
the chemical equivalent is the number of moles of electron transferred.
N= n x M, where n is the no of moles of proton exchange in a reaction.
N = n mole equivalents / L solution
The normality of HCl, is the same as the molarity of HCl because there is one mole of H+ ions for
every one mole of HCl. The normality of H2SO4 is twice the molarity because there are two
moles of H+ per mole of sulfuric acid. Normality has the advantage of giving effective
concentration (3M H2SO4 is twice as acidic as 3M HCl - this is clear if they are labeled 6N and
3N, respectively.
Formality
The formal concentration refers to the amount of substance dissolved without regard to its actual
composition in solution. If a solution is made by diluting 1.00 mol of HBr to 1.00L with water,
the formal concentration of HBr is 1.00mole per liter. But the actual concentration of HBr is
nearly zero because the HBr molecules have dissociated. Rather than calling the HBr solution
1.00M, it would be more correct to call it 1.00F.
Sometimes used interchangeably with Molarity, in actual sense it is not so. Unless you are fully
aware of the chemistry of a particular compound, you rarely know its molarity, but you can know
its formal concentration from the amount weighed into a solution by analytical procedure, for
this reason, formal concentration is also known as analytical concentration.
F = n formula weight unit/ L solution.
Conversion among Units
1. Percent Composition to Molarity
In order to convert mass percent to molarity or vice versa, you need to know the density of
the solution; this gives you a mass of the solution and a mass of solute. Use the density to
find the volume of the solution. Use dimensional analysis to convert the mass of the solute to
moles. Parts per million and billion can be worked the same way except for the decimal
point.
Example
Concentrated hydrochloric acid is 31% hydrochloric acid and 69% water, by mass. If the
density of concentrated HCL is 1.16g/mL. What is the Molarity? If the formula weight of
HCl is 36.45 g/mol
Assume that 100g of concentrated HCl has 31g of HCL and 69 g of water.
No of moles of HCl = 31g/36.45g/mol = 0.85mol
 Density = Mass/ Volume
V = M/D = 100g/ 1.16g/mL = 86.2mL = 0.0862L
Molarity = No of moles / volume = 0.85 mol/0,0826L = 12mol/L == 12M
2. Mole Fraction to Molarity
An aqueous solution of sulfuric acid has a molarity of 18mol/L. If its density is 1.84
g/mL, what is the mole fraction of water in the solution? Formula weight of H2SO4 is
98.08 g/mol
Assume one liter of solution, which has 18 moles of sulfuric acid. The formula weight of
sulfuric acid is 98.08 g/mol, so 18 moles of the acid has a mass of 1800g (1756 with two
significant figures). Use density to find the mass of the solution.
OR
1 mole = 98.08 g/mol
Therefore 18 moles will have a mass = 18 mol x 98.08 g/mol = 1765.4 rounded to 2 sig.
fig. =1800g
D = M/V
M= D x V = 1.85g /mL x 1000mL == 1840 meaning that out of 1840g, 1800g is the mass
of sulfuric acid and 40g the mass of water. If the formula weight of water is 18.013
g/mol, we can only have 2mols of water
XH2O (mole fraction of H2O) = 2mol/ 18 mol + 2 mol = 0.1 mol
3. Molarity to Molality
An aqueous solution of hydrogen peroxide is 16.9 mol / L, it has a density of 1.196g/mL, what
is its molality?
Solution:
Assume one liter of solution, this has 16.9 moles of Hydrogen peroxide. The formula weight of
Hydrogen peroxide is 34.015 g/mol.
Mass of the solution = D x V == 1.196g/mL x 1000mL = 1196g
Mass of Hydrogen peroxide in the solution will be
1 mole of H2O2 = 34.015g/mol
Therefore, 16.9 mole mass will be == 34.015 g/mol X 16.9 mol = 575g of H2O2
If the mixture has 575g of H2O2 in 1196 g of solution, 621 will be the mass of water (solvent).
The molality is
M == 16.9mol/ 0.621kg (621g converted to kg) = 27.2mol/kg
4. Normality and Formality
What is the normality and formality of concentrated sulfuric acid, 18M?
Answer: Sulfuric acid has two H= in its formula, so one mole solute has two moles of
equivalents. Concentrated sulfuric acid has a normality of 36N. The number of gram formula
weights for sulfuric is the same as the number of moles of solute, so concentrated sulfuric acid
has a formality of 18F.
How to Calculate Dilutions
You dilute a solution whenever you add solvent to a solution. Adding solvent results in a
solution of lower concentration. You can calculate the concentration of a solution following a
dilution by applying this equation:
MiVi = MfVf

Where M is molarity, V is volume, and the subscripts i and f refer to the initial and final values.
Example:
How many milliliters of 5.5 M NaOH are needed to prepare 300 mL of 1.2 M NaOH?
Solution:
5.5 M x V1 = 1.2 M x 0.3 L
V1 = 1.2 M x 0.3 L / 5.5 M
V1 = 0.065 L
V1 = 65 mL

Part Per Million (PPM)

Composition is often expressed as parts per million (ppm), parts per billion (ppb) or parts per
thousand. The term one part per million, for example indicates that one gram of the substance of
interest is present per million grams of total solution or mixture
i.e
1 g of substance
6 OR g ofg substance
of sample 10
−6
1 x 10 g of sample
1 gram of substance
ppt =g ofg substance
of sample 10
−3
Or
1 x 103 of sample
g of substance
ppb == Or g ofg substance
of sample 10
−9
1 x 109 of sample

Examples

1. Convert 1ppm to 1 µg/mL

1 ppm = 1 part of substance / 1 x 106 part of solution

= 1 g of X / 1 x 106 of solution

= 1 x 10-6 / g of solution

= 1µg of X (i.e Substance) / g of solution = µg/ g

If the solution is in water and the density of water is 1 g / mL, then

1 ppm = 1 µg/ mL solution

2. Example 2

A solution contains Cu2+ ions at a concentration of 3 X 10 -4

M. What is the Cu2+
concentration in ppm?
Recall1 ppm = 1 µg/ mL solution, but molarity uses moles / L, so the mL need to be
converted to L

1 ppm = 1 µg X / mL solution x 10-3 L/mL…. converting mL to L

= 1000 µg X / L solution. Note 1000 µg is 1 mg

= mg /L solution

We know that molarity of the solution is in moles /L

**We need to convert moles to mg

moles /L Cu2+ = 3 x 10 -4 M, i. e M is mole/L

Molar mass of Cu = 63.55g / mole

mole g
moles /L of Cu2+ = 3 x 10-4 x 63.55 = 1.9x 10-2 g / L
L mole

But we want mg of Cu2+, so convert g to milligram

1000mg = 1g

Thus, 1.9 x 10-2 x 1000mg /L = 1.9mg / L, since 1 ppm == 1 mg/ L

Moles / L of Cu2+ = 1.9 ppm

How to convert ppm to percent

1% = 1/100

1ppm = 1 / 1,000,000

So 1ppm = 0.0001% i.e 1 / 1,000,000 X 100 = 0.0001%

So to convert ppm to percent, divide the ppm by 10,000

X% = X (ppm)/ 10,000

Example

Find how many percent are in 300ppm.

X (%) = 300ppm 10,000 = 0.03%

Convert 5% to ppm

5/100 x 1,000,000 = 50,000ppm

50.000 ppm/ 10,000 = 5%

Assignments

1. A solution is made by dissolving 12.00 g of benzene C6H6 in enough hexane to give 20.0
mL of solution. Find the molarity of the benzene.
2. Commercial concentrated HCl is labelled 37% which you may assume means weight
percent. Its density, sometimes called specific gravity is 1.18g/mL. Find a. the molarity of
the HCl, b. mass of solution containing 0.100mole of HCl and C. the volume of solution
containing 1.00mol of HCl.
3. What quantity of H2C2O4. 2H2O (Oxalic acid dihydrate) should be used to prepare 250mL
of 150M of the acid.
4. B (a) P is a carcinogen and it was found that the source to human is from air and was
determined to be 1ppm. What this concentration is as measured in mg/m 3 in the
atmosphere?

References

1. Daniel C. Harris; Quantitative Chemical Analysis, Third Edition. W. H. Freeman and

Company, New York
2. G.H Jeffery, J. Bassett, J. Mendham, R.C Denny: VOGEL’S textbook of Quantitative
Chemical Analysis. Fifth Edition, Longman Scientific and Technical. John wiley and
Sons, Inc., New York