Elemental Analysis and Calculations

● The process of determining the molecular formula of a new compounds typically begins by findings its
percent composition
● The percent composition of a compound identifies what elements are present and how much of each
element is present
● Traditionally combustion analysis used to determine the percent composition of a substance
● In combustion analysis the substance is first burned in the presence of a stream of oxygen to produce
CO2 and H2O
○ The percent hydrogen is determined from the mass of H2O absorbed by MgClO4
○ The percent carbon is determined from the mass of CO2 absorbed by sodium hydroxide
○ In a sample containing only C, H, and O the amount of oxygen typically determined by
difference
● Requirements for the accuracy and precision of combustion analysis results
● To be acceptable for publication, most journals require found percentages to be less than 0.4% off of
their calculated values
● Acceptable results should be good to two decimal places
○ Results should have four significant figures if the percentage is between 10 and 100
○ Results should have three significant figures if the percentage is between 0 and 10
● More modern techniques use gas chromatography to detect the relative amounts of gasses produced
during combustion analysis.
● Gas chromatography techniques detect various elements as the following gases
○ Carbon and hydrogen are still detected as carbon dioxide and water respectively
○ Sulfur is detected as the gas sulfur dioxide.
○ Combustion of nitrogen affords nitrogen oxides that are chemically reduced to nitrogen gas and
detected
○ Oxygen may be detected by ignition of the sample in an atmosphere of hydrogen gas to
produce water.
● Knowing a compound’s percent composition makes it possible to calculate the compounds empirical
formula.
○ The strategy is to first find the relative number of moles of each element and use those numbers
to determine the mole ratios of the elements
○ The mole ratios, in turn, correspond to the subscripts in the compound's empirical formula

Determination of Molecular Mass

● An empirical formula is the simplest positive integer ratio of atoms present in a molecule (only tells us
the ratio of atoms in a compound)
● A compounds molecular formula tells us the actual numbers of atoms in a molecule (may be the same
as the empirical formula or a multiple of it)
● To determine a compounds molecular formula from its empirical formula, we must know its molecular
weight
 ○ Recall the molecular weight of a compound is the sum of atomic weights of all atoms in a
molecule
● Vapor Density Method
○ Molecular mass calculated from the mole fraction of a known weight and volume of gas at
standard temperature and pressure
● Cryoscopic (freezing point depression) Method
○ Measurement of the freezing point depression that is brought about by addition of a known
quantity of test substance
● Vapor Pressure Osmometry
○ The molecular weight of a substance is determined through an examination of the change in
vapor pressure when a test substance is dissolved in it.
● Often the empirical formula weight and the molecular mass are the same
○ In such cases, the empirical formula weight is the also the molecular formula
● When the empirical formula weight is less than the molecular weight, it is necessary to determine how
many times the empirical formula weight may be divided into the molecular mass

Index of Hydrogen Deficiency

● The maximum number of hydrogen atoms in organic compounds may be determined based on the
number of carbon atoms using the following formulas
● Notice each time a ring or p bond is introduced into a molecule, the number of hydrogens in the
molecular formula is reduced by two
● Consequently, for organic compounds containing only carbon and hydrogen, the index of hydrogen

deficiency may be expressed as: where: U = The number of rings and/or

p bonds, C = The number of carbon atoms, H = The number of hydrogen atoms
○ Because the halogens (F, Cl, Br, I) are monovalent,one binding position is lost for each halogen
■ consequently the maximum number of hydrogens is reduced by one
○ Because group VI atoms (O, S, Se)are divalent , one binding position is lost while one is gained
■ consequently no adjustment in the maximum number of hydrogens is required
○ Because group V elements (N & P) are trivalent , one bindng position is lost while two binding
positions are gained
■ Consequently the maximum number of hydrogens increases by one
● The index of hydrogen deficiency may also be determined from the valences of the atoms in the

molecule where: U = The number of rings and/or p bonds, ni = The number of

atoms n, vi = The valence (number of lone pairs) of atom n

The Rule of Thirteen

● A method for generating all possible molecular formulas for a given molecular mass where:

U = The number of rings and/or p bonds, ni = The number of atoms n, vi = The

valence (number of lone pairs) of atom n
● The first step involves generation of a base formula which contains only carbon and hydrogen
○ The base formula is found by dividing the molecular weight MW by 13 (the mass of one carbon

and one hydrogen)

○ The numerator n represents the number of carbon atoms while the sum n + r represents the
number of hydrogen atoms that has the desired molecular weight M.W.
● The index of hydrogen deficiency (unsaturation ) U that corresponds to the proceding formula is

calculated easily by applying the relationship

● To derive a molecular formula that includes other atoms besides carbon and hydrogen, subtract the
mass of a combination of carbon and hydrogen atoms that equals the masses of the other atoms being
included
● Table of carbon/hydrogen equivalents for some common elements

● Subtraction of the product n times 13 from the MW gives remainder r

○ Since 13 is the weight of one carbon and one hydrogen atom, “r” is the number of extra
hydrogens needed to achieve the proper MW
● The total number of hydrogens is then obtained by addition of “n” and the remainder “r”
○ Addition of “r” to “n” gives the total number of hydrogens present
● Special attention should be paid to the index of hydrogen deficiency calculation
○ Impossible index of hydrogen deficiencies (negative or fractional) can lead to the rejection of
one or more possible chemical formulas
○ Ex: benzamide (C9H12), IHD = 3.5
■ Since this formula has an impossible IHD (IHD cannot be a fraction) and the molecular
ion has an odd mass
 ■ It is reasonable to add nitrogen to the formula (subtracting CH2) resulting in a new
formula of C8H11N (IHD = 4)
■ Other possible formulas involving nitrogen and oxygen are C6H7N3 (IHD = 5) and
C7H7NO (IHD =5)
■ Other spectral evidence (IR and NMR) may identify specific elements to include and a
correct structure for the formula
● Observe how for a low molecular mass the inference of big elements simplifies the number of possible
structures
○ Base formula: C7H14
■ Add nitrogen: C6H12N (sub CH2)
■ Index of Hydrogen Deficiency: 1.5
■ Probably an incorrect formula, it is unlikely the compound has nitrogen
○ Base formula: C7H14
■ Add sulfur: C5H6S (sub C2H8)
■ Index of Hydrogen Deficiency: 3
■ Very few possibilities with only 6 hydrogens and an index of hydrogen deficiency of 3
○ Base formula: C7H14
■ Add Bromine: CH7Br (sub C6H7)
■ Index of Hydrogen Deficiency: -2
■ Impossible structure